Quantal Study of the Exchange Reaction for N + N2 using an ab initio Potential Energy Surface

NASA Technical Reports Server (NTRS)

Wang, Dunyou; Stallcop, James R.; Huo, Winifred M.; Dateo, Christopher E.; Schwenke, David W.; Partridge, Harry; Kwak, Dochan (Technical Monitor)

2002-01-01

The N + N2 exchange rate is calculated using a time-dependent quantum dynamics method on a newly determined ab initio potential energy surface (PES) for the ground A" state. This ab initio PES shows a double barrier feature in the interaction region with the barrier height at 47.2 kcal/mol, and a shallow well between these two barriers, with the minimum at 43.7 kcal/mol. A quantum dynamics wave packet calculation has been carried out using the fitted PES to compute the cumulative reaction probability for the exchange reaction of N + N2(J=O). The J - K shift method is then employed to obtain the rate constant for this reaction. The calculated rate constant is compared with experimental data and a recent quasi-classical calculation using a LEPS PES. Significant differences are found between the present and quasiclassical results. The present rate calculation is the first accurate 3D quantal dynamics study for N + N2 reaction system and the ab initio PES reported here is the first such surface for N3.

NMR studies on the structure and dynamics of lac operator DNA

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

Lee, S.C.

Nuclear Magnetic Resonance spectroscopy was used to elucidate the relationships between structure, dynamics and function of the gene regulatory sequence corresponding to the lactose operon operator of Escherichia coli. The length of the DNA fragments examined varied from 13 to 36 base pair, containing all or part of the operator sequence. These DNA fragments are either derived genetically or synthesized chemically. Resonances of the imino protons were assigned by one dimensional inter-base pair nuclear Overhauser enhancement (NOE) measurements. Imino proton exchange rates were measured by saturation recovery methods. Results from the kinetic measurements show an interesting dynamic heterogeneity with amore » maximum opening rate centered about a GTG/CAC sequence which correlates with the biological function of the operator DNA. This particular three base pair sequence occurs frequently and often symmetrically in prokaryotic nd eukaryotic DNA sites where one anticipates specific protein interaction for gene regulation. The observed sequence dependent imino proton exchange rate may be a reflection of variation of the local structure of regulatory DNA. The results also indicate that the observed imino proton exchange rates are length dependent.« less

Time-series analysis of multiple foreign exchange rates using time-dependent pattern entropy

NASA Astrophysics Data System (ADS)

Ishizaki, Ryuji; Inoue, Masayoshi

2018-01-01

Time-dependent pattern entropy is a method that reduces variations to binary symbolic dynamics and considers the pattern of symbols in a sliding temporal window. We use this method to analyze the instability of daily variations in multiple foreign exchange rates. The time-dependent pattern entropy of 7 foreign exchange rates (AUD/USD, CAD/USD, CHF/USD, EUR/USD, GBP/USD, JPY/USD, and NZD/USD) was found to be high in the long period after the Lehman shock, and be low in the long period after Mar 2012. We compared the correlation matrix between exchange rates in periods of high and low of the time-dependent pattern entropy.

The performance of one belt and one road exchange rate: Based on improved singular spectrum analysis

NASA Astrophysics Data System (ADS)

Lai, Lin; Guo, Kun

2017-10-01

;One Belt and One Road; strategy in China is on push of foreign trade openness at northwest, southwest and northeast, absorption of the excess capacity and new support for economic increase. However, the fluctuation in RMB exchange rate with the countries along the road is unstable so related Chinese enterprises will face high risk of exchange rate. Precise explanation or prediction for exchange rate has been the challengeable hop point in the international finance. This paper decomposed the One Belt One Road Exchange Rate Index (OBORR) and the RMB Effective Exchange Rate Index (CNYX) into trend term, market fluctuation term and noise term using improved singular spectrum analysis (SSA). It turns out that the increasing velocity of OBORR is greater than that of CNYX in the long term, and there is dynamic lead-lag structure in the medium term. In the short term, the fluctuation range and frequency of OBORR are greater than those of CNYX, which means there will be more exchange rate risks in One Belt and One Road countries.

Probing dynamics and mechanism of exchange process of quaternary ammonium dimeric surfactants, 14-s-14, in the presence of conventional surfactants.

PubMed

Liu, Jun; Jiang, Yan; Chen, Hong; Mao, Shi Zhen; Du, You Ru; Liu, Mai Li

2012-12-27

In this Article, we investigated effects of different types of conventional surfactants on exchange dynamics of quaternary ammonium dimeric surfactants, with chemical formula C(14)H(29)N(+)(CH(3))(2)- (CH(2))(s)-N(+)(CH(3))(2)C(14)H(29)·2Br(-), or 14-s-14 for short. Two nonionic surfactants, TritonX-100 (TX-100) and polyethylene glycol (23) laurylether (Brij-35), and one cationic surfactant, n-tetradecyltrimethyl ammonium bromide (TTAB), and one ionic surfactant, sodium dodecyl sulfate (SDS) were chosen as typical conventional surfactants. Exchange rates of 14-s-14 (s = 2, 3, and 4) between the micelle form and monomer in solution were detected by two NMR methods: one-dimensional (1D) line shape analysis and two-dimensional (2D) exchange spectroscopy (EXSY). Results show that the nonionic surfactants (TX-100 and Brij-35), the cationic surfactant (TTAB), and the ionic surfactant (SDS) respectively accelerated, barely influenced, and slowed the exchange rate of 14-s-14. The effect mechanism was investigated by the self-diffusion experiment, relaxation time measurements (T(2)/T(1)), the fluorescence experiment (I(1)/I(3)) and observed chemical shift variations. Results reveal that, nonionic conventional surfactants (TX-100 and Brij-35) loosened the molecule arrangement and decreased hydrophobic interactions in the micelle, and thus accelerated the exchange rate of 14-s-14. The cationic conventional surfactant (TTAB) barely changed the molecule arrangement and thus barely influenced the exchange rate of 14-s-14. The ionic conventional surfactant (SDS) introduced the electrostatic attraction effect, tightened the molecule arrangement, and increased hydrophobic interactions in the micelle, and thus slowed down the exchange rate of 14-s-14. Additionally, the two-step exchange mechanism of 14-s-14 in the mixed solution was revealed through interesting variation tendencies of exchange rates of 14-s-14.

Dual Rate Adaptive Control for an Industrial Heat Supply Process Using Signal Compensation Approach

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

Chai, Tianyou; Jia, Yao; Wang, Hong

The industrial heat supply process (HSP) is a highly nonlinear cascaded process which uses a steam valve opening as its control input, the steam flow-rate as its inner loop output and the supply water temperature as its outer loop output. The relationship between the heat exchange rate and the model parameters, such as steam density, entropy, and fouling correction factor and heat exchange efficiency are unknown and nonlinear. Moreover, these model parameters vary in line with steam pressure, ambient temperature and the residuals caused by the quality variations of the circulation water. When the steam pressure and the ambient temperaturemore » are of high values and are subjected to frequent external random disturbances, the supply water temperature and the steam flow-rate would interact with each other and fluctuate a lot. This is also true when the process exhibits unknown characteristic variations of the process dynamics caused by the unexpected changes of the heat exchange residuals. As a result, it is difficult to control the supply water temperature and the rates of changes of steam flow-rate well inside their targeted ranges. In this paper, a novel compensation signal based dual rate adaptive controller is developed by representing the unknown variations of dynamics as unmodeled dynamics. In the proposed controller design, such a compensation signal is constructed and added onto the control signal obtained from the linear deterministic model based feedback control design. Such a compensation signal aims at eliminating the unmodeled dynamics and the rate of changes of the currently sample unmodeled dynamics. A successful industrial application is carried out, where it has been shown that both the supply water temperature and the rate of the changes of the steam flow-rate can be controlled well inside their targeted ranges when the process is subjected to unknown variations of its dynamics.« less

A note on the theory of fast money flow dynamics

NASA Astrophysics Data System (ADS)

Sokolov, A.; Kieu, T.; Melatos, A.

2010-08-01

The gauge theory of arbitrage was introduced by Ilinski in [K. Ilinski, preprint arXiv:hep-th/9710148 (1997)] and applied to fast money flows in [A. Ilinskaia, K. Ilinski, preprint arXiv:cond-mat/9902044 (1999); K. Ilinski, Physics of finance: gauge modelling in non-equilibrium pricing (Wiley, 2001)]. The theory of fast money flow dynamics attempts to model the evolution of currency exchange rates and stock prices on short, e.g. intra-day, time scales. It has been used to explain some of the heuristic trading rules, known as technical analysis, that are used by professional traders in the equity and foreign exchange markets. A critique of some of the underlying assumptions of the gauge theory of arbitrage was presented by Sornette in [D. Sornette, Int. J. Mod. Phys. C 9, 505 (1998)]. In this paper, we present a critique of the theory of fast money flow dynamics, which was not examined by Sornette. We demonstrate that the choice of the input parameters used in [K. Ilinski, Physics of finance: gauge modelling in non-equilibrium pricing (Wiley, 2001)] results in sinusoidal oscillations of the exchange rate, in conflict with the results presented in [K. Ilinski, Physics of finance: gauge modelling in non-equilibrium pricing (Wiley, 2001)]. We also find that the dynamics predicted by the theory are generally unstable in most realistic situations, with the exchange rate tending to zero or infinity exponentially.

Methanol exchange dynamics between a temperate cropland soil and the atmosphere

NASA Astrophysics Data System (ADS)

Bachy, A.; Aubinet, M.; Amelynck, C.; Schoon, N.; Bodson, B.; Moureaux, C.; Delaplace, P.; De Ligne, A.; Heinesch, B.

2018-03-01

Soil methanol (CH3OH) exchange is often considered as several orders of magnitude smaller than plant methanol exchange. However, for some ecosystems, it is significant in regard with plant exchange and worth thus better consideration. Our study sought to gain a better understanding of soil exchange. Methanol flux was measured at the ecosystem scale on a bare agricultural soil over two contrasted periods using the disjunct eddy covariance by mass scanning technique. A proton-transfer-reaction mass spectrometer was used for the methanol ambient mixing ratio measurements. Bi-directional exchange dynamics were observed. Methanol emission occurred under dry and warm conditions and correlated best with soil surface temperature, whereas methanol uptake occurred under wet and mild conditions and correlated well with the methanol ambient concentration. After having tested a physical adsorption-desorption model and by confronting our data with the literature, we propose that the exchange was ruled by both a physical adsorption/desorption mechanism and by a methanol source, which still needs to be identified. The soil emission decreased when the vegetation developed. The reasons for the decrease still need to be determined. Overall, the dynamics observed at our site were similar to those reported by other studies for both cropland and forest ecosystems. The mechanism proposed in our work can thus be possibly applied to other sites or ecosystems. In addition, the methanol exchange rate was in the upper range of the exchange rates reported by other soil studies, suggesting that cropland soils are more important methanol exchangers than those in other ecosystems and should therefore be further investigated.

Kinetics from Replica Exchange Molecular Dynamics Simulations.

PubMed

Stelzl, Lukas S; Hummer, Gerhard

2017-08-08

Transitions between metastable states govern many fundamental processes in physics, chemistry and biology, from nucleation events in phase transitions to the folding of proteins. The free energy surfaces underlying these processes can be obtained from simulations using enhanced sampling methods. However, their altered dynamics makes kinetic and mechanistic information difficult or impossible to extract. Here, we show that, with replica exchange molecular dynamics (REMD), one can not only sample equilibrium properties but also extract kinetic information. For systems that strictly obey first-order kinetics, the procedure to extract rates is rigorous. For actual molecular systems whose long-time dynamics are captured by kinetic rate models, accurate rate coefficients can be determined from the statistics of the transitions between the metastable states at each replica temperature. We demonstrate the practical applicability of the procedure by constructing master equation (Markov state) models of peptide and RNA folding from REMD simulations.

Sampling of Protein Folding Transitions: Multicanonical Versus Replica Exchange Molecular Dynamics.

PubMed

Jiang, Ping; Yaşar, Fatih; Hansmann, Ulrich H E

2013-08-13

We compare the efficiency of multicanonical and replica exchange molecular dynamics for the sampling of folding/unfolding events in simulations of proteins with end-to-end β -sheet. In Go-model simulations of the 75-residue MNK6, we observe improvement factors of 30 in the number of folding/unfolding events of multicanonical molecular dynamics over replica exchange molecular dynamics. As an application, we use this enhanced sampling to study the folding landscape of the 36-residue DS119 with an all-atom physical force field and implicit solvent. Here, we find that the rate-limiting step is the formation of the central helix that then provides a scaffold for the parallel β -sheet formed by the two chain ends.

Assessing inefficiency in euro bilateral exchange rates

NASA Astrophysics Data System (ADS)

Tabak, Benjamin M.; Cajueiro, Daniel O.

2006-07-01

This paper assesses inefficiency for 10 euro bilateral exchange rates. We study the dynamics of these time series by estimating Tsallis q entropic index and Hurst exponents using the local Whittle estimator. Empirical results suggest that US, Canadian and Singapore dollar are amongst the most efficient currencies, while Japanese yen and Swedish krona are amongst the most inefficient.

Fluctuation dynamics of exchange rates on Polish financial market

NASA Astrophysics Data System (ADS)

Orłowski, A.; Struzik, Z. R.; Syczewska, E.; Załuska-Kotur, M. A.

2004-12-01

We show results of local fluctuation analysis, probability distributions, and fractional integration analysis for nominal exchange rates of the Polish zloty versus two foreign currencies (US dollar and German mark/euro). The results confirm the rapid change of the volatility pattern in August 1997. We compare the type of the fluctuation behavior before and after this date.

Dynamic Models of Learning That Characterize Parent-Child Exchanges Predict Vocabulary Growth

ERIC Educational Resources Information Center

Ober, David R.; Beekman, John A.

2016-01-01

Cumulative vocabulary models for infants and toddlers were developed from models of learning that predict trajectories associated with low, average, and high vocabulary growth rates (14 to 46 months). It was hypothesized that models derived from rates of learning mirror the type of exchanges provided to infants and toddlers by parents and…

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

Roy, Santanu; Dang, Liem X.

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

Dynamic Response of Exchange Bias in Graphene Nanoribbons

DTIC Science & Technology

2012-01-01

in establishing the GNRs-based spintronic devices. Keywords: Dynamic magnetic properties , exchange bias, training effect, field sweep rate and...transport properties by means of various applied conditions 6, 7 . The discovery 8 of weak ferromagnetism in polymerized C60 has invoked a special...attention to investigate the magnetic properties of carbon- based materials. Graphene is an allotrope of carbon and irradiation of graphene with ions

Chain exchange in triblock copolymer micelles

NASA Astrophysics Data System (ADS)

Lu, Jie; Lodge, Timothy; Bates, Frank

2015-03-01

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

Foreign exchange rate entropy evolution during financial crises

NASA Astrophysics Data System (ADS)

Stosic, Darko; Stosic, Dusan; Ludermir, Teresa; de Oliveira, Wilson; Stosic, Tatijana

2016-05-01

This paper examines the effects of financial crises on foreign exchange (FX) markets, where entropy evolution is measured for different exchange rates, using the time-dependent block entropy method. Empirical results suggest that financial crises are associated with significant increase of exchange rate entropy, reflecting instability in FX market dynamics. In accordance with phenomenological expectations, it is found that FX markets with large liquidity and large trading volume are more inert - they recover quicker from a crisis than markets with small liquidity and small trading volume. Moreover, our numerical analysis shows that periods of economic uncertainty are preceded by periods of low entropy values, which may serve as a tool for anticipating the onset of financial crises.

Multivariable nonlinear analysis of foreign exchange rates

NASA Astrophysics Data System (ADS)

Suzuki, Tomoya; Ikeguchi, Tohru; Suzuki, Masuo

2003-05-01

We analyze the multivariable time series of foreign exchange rates. These are price movements that have often been analyzed, and dealing time intervals and spreads between bid and ask prices. Considering dealing time intervals as event timing such as neurons’ firings, we use raster plots (RPs) and peri-stimulus time histograms (PSTHs) which are popular methods in the field of neurophysiology. Introducing special processings to obtaining RPs and PSTHs time histograms for analyzing exchange rates time series, we discover that there exists dynamical interaction among three variables. We also find that adopting multivariables leads to improvements of prediction accuracy.

An alternative way to track the hot money in turbulent times

NASA Astrophysics Data System (ADS)

Sensoy, Ahmet

2015-02-01

During recent years, networks have proven to be an efficient way to characterize and investigate a wide range of complex financial systems. In this study, we first obtain the dynamic conditional correlations between filtered exchange rates (against US dollar) of several countries and introduce a time-varying threshold correlation level to define dynamic strong correlations between these exchange rates. Then, using evolving networks obtained from strong correlations, we propose an alternative approach to track the hot money in turbulent times. The approach is demonstrated for the time period including the financial turmoil of 2008. Other applications are also discussed.

Modeling the demand-price relations in a high-frequency foreign exchange market

NASA Astrophysics Data System (ADS)

Schmidt, Anatoly B.

1999-09-01

A stochastic nonlinear dynamics model is introduced in terms of observable variables (price and excess demand assumed to be proportional to the number of buyers) to describe a high-frequency foreign exchange market. It is shown how the fundamentalist and chartist patterns of the trader behavior affect the correlation between excess demand and exchange rates.

Does implied volatility of currency futures option imply volatility of exchange rates?

NASA Astrophysics Data System (ADS)

Wang, Alan T.

2007-02-01

By investigating currency futures options, this paper provides an alternative economic implication for the result reported by Stein [Overreactions in the options market, Journal of Finance 44 (1989) 1011-1023] that long-maturity options tend to overreact to changes in the implied volatility of short-maturity options. When a GARCH process is assumed for exchange rates, a continuous-time relationship is developed. We provide evidence that implied volatilities may not be the simple average of future expected volatilities. By comparing the term-structure relationship of implied volatilities with the process of the underlying exchange rates, we find that long-maturity options are more consistent with the exchange rates process. In sum, short-maturity options overreact to the dynamics of underlying assets rather than long-maturity options overreacting to short-maturity options.

A dynamic analysis of S&P 500, FTSE 100 and EURO STOXX 50 indices under different exchange rates.

PubMed

Chen, Yanhua; Mantegna, Rosario N; Pantelous, Athanasios A; Zuev, Konstantin M

2018-01-01

In this study, we assess the dynamic evolution of short-term correlation, long-term cointegration and Error Correction Model (hereafter referred to as ECM)-based long-term Granger causality between each pair of US, UK, and Eurozone stock markets from 1980 to 2015 using the rolling-window technique. A comparative analysis of pairwise dynamic integration and causality of stock markets, measured in common and domestic currency terms, is conducted to evaluate comprehensively how exchange rate fluctuations affect the time-varying integration among the S&P 500, FTSE 100 and EURO STOXX 50 indices. The results obtained show that the dynamic correlation, cointegration and ECM-based long-run Granger causality vary significantly over the whole sample period. The degree of dynamic correlation and cointegration between pairs of stock markets rises in periods of high volatility and uncertainty, especially under the influence of economic, financial and political shocks. Meanwhile, we observe the weaker and decreasing correlation and cointegration among the three developed stock markets during the recovery periods. Interestingly, the most persistent and significant cointegration among the three developed stock markets exists during the 2007-09 global financial crisis. Finally, the exchange rate fluctuations, also influence the dynamic integration and causality between all pairs of stock indices, with that influence increasing under the local currency terms. Our results suggest that the potential for diversifying risk by investing in the US, UK and Eurozone stock markets is limited during the periods of economic, financial and political shocks.

Toward structural dynamics: protein motions viewed by chemical shift modulations and direct detection of C'N multiple-quantum relaxation.

PubMed

Mori, Mirko; Kateb, Fatiha; Bodenhausen, Geoffrey; Piccioli, Mario; Abergel, Daniel

2010-03-17

Multiple quantum relaxation in proteins reveals unexpected relationships between correlated or anti-correlated conformational backbone dynamics in alpha-helices or beta-sheets. The contributions of conformational exchange to the relaxation rates of C'N coherences (i.e., double- and zero-quantum coherences involving backbone carbonyl (13)C' and neighboring amide (15)N nuclei) depend on the kinetics of slow exchange processes, as well as on the populations of the conformations and chemical shift differences of (13)C' and (15)N nuclei. The relaxation rates of C'N coherences, which reflect concerted fluctuations due to slow chemical shift modulations (CSMs), were determined by direct (13)C detection in diamagnetic and paramagnetic proteins. In well-folded proteins such as lanthanide-substituted calbindin (CaLnCb), copper,zinc superoxide dismutase (Cu,Zn SOD), and matrix metalloproteinase (MMP12), slow conformational exchange occurs along the entire backbone. Our observations demonstrate that relaxation rates of C'N coherences arising from slow backbone dynamics have positive signs (characteristic of correlated fluctuations) in beta-sheets and negative signs (characteristic of anti-correlated fluctuations) in alpha-helices. This extends the prospects of structure-dynamics relationships to slow time scales that are relevant for protein function and enzymatic activity.

Estimating time-varying conditional correlations between stock and foreign exchange markets

NASA Astrophysics Data System (ADS)

Tastan, Hüseyin

2006-02-01

This study explores the dynamic interaction between stock market returns and changes in nominal exchange rates. Many financial variables are known to exhibit fat tails and autoregressive variance structure. It is well-known that unconditional covariance and correlation coefficients also vary significantly over time and multivariate generalized autoregressive model (MGARCH) is able to capture the time-varying variance-covariance matrix for stock market returns and changes in exchange rates. The model is applied to daily Euro-Dollar exchange rates and two stock market indexes from the US economy: Dow-Jones Industrial Average Index and S&P500 Index. The news impact surfaces are also drawn based on the model estimates to see the effects of idiosyncratic shocks in respective markets.

NMR Analysis of Amide Hydrogen Exchange Rates in a Pentapeptide-Repeat Protein from A. thaliana.

PubMed

Xu, Shenyuan; Ni, Shuisong; Kennedy, Michael A

2017-05-23

At2g44920 from Arabidopsis thaliana is a pentapeptide-repeat protein (PRP) composed of 25 repeats capped by N- and C-terminal α-helices. PRP structures are dominated by four-sided right-handed β-helices typically consisting of mixtures of type II and type IV β-turns. PRPs adopt repeated five-residue (Rfr) folds with an Rfr consensus sequence (STAV)(D/N)(L/F)(S/T/R)(X). Unlike other PRPs, At2g44920 consists exclusively of type II β-turns. At2g44920 is predicted to be located in the thylakoid lumen although its biochemical function remains unknown. Given its unusual structure, we investigated the biophysical properties of At2g44920 as a representative of the β-helix family to determine if it had exceptional global stability, backbone dynamics, or amide hydrogen exchange rates. Circular dichroism measurements yielded a melting point of 62.8°C, indicating unexceptional global thermal stability. Nuclear spin relaxation measurements indicated that the Rfr-fold core was rigid with order parameters ranging from 0.7 to 0.9. At2g44920 exhibited a striking range of amide hydrogen exchange rates spanning 10 orders of magnitude, with lifetimes ranging from minutes to several months. A weak correlation was found among hydrogen exchange rates, hydrogen bonding energies, and amino acid solvent-accessible areas. Analysis of contributions from fast (approximately picosecond to nanosecond) backbone dynamics to amide hydrogen exchange rates revealed that the average order parameter of amides undergoing fast exchange was significantly smaller compared to those undergoing slow exchange. Importantly, the activation energies for amide hydrogen exchange were found to be generally higher for the slowest exchanging amides in the central Rfr coil and decreased toward the terminal coils. This could be explained by assuming that the concerted motions of two preceding or following coils required for hydrogen bond disruption and amide hydrogen exchange have a higher activation energy compared to that required for displacement of a single coil to facilitate amide hydrogen exchange in either the terminal or penultimate coils. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Conformational exchange in pseudoazurin: different kinds of microsecond to millisecond dynamics characterized by their pH and buffer dependence using 15N NMR relaxation.

PubMed

Hass, Mathias A S; Vlasie, Monica D; Ubbink, Marcellus; Led, Jens J

2009-01-13

The dynamics of the reduced form of the blue copper protein pseudoazurin from Alcaligenes faecalis S-6 was investigated using (15)N relaxation measurements with a focus on the dynamics of the micro- to millisecond time scale. Different types of conformational exchange processes are observed in the protein on this time scale. At low pH, the protonation of the C-terminal copper-ligated histidine, His81, is observed. A comparison of the exchange rates in the presence and absence of added buffers shows that the protonation is the rate-limiting step at low buffer concentrations. This finding agrees with previous observations for other blue copper proteins, e.g., amicyanin and plastocyanin. However, in contrast to plastocyanin but similar to amicyanin, a second conformational exchange between different conformations of the protonated copper site is observed at low pH, most likely triggered by the protonation of His81. This process has been further characterized using CPMG dispersion methods and is found to occur with a rate of a few thousands per second. Finally, micro- to millisecond motions are observed in one of the loop regions and in the alpha-helical regions. These motions are unaffected by pH and are unrelated to the conformational changes in the active site of pseudoazurin.

Instrumentation for cryogenic magic angle spinning dynamic nuclear polarization using 90 L of liquid nitrogen per day

NASA Astrophysics Data System (ADS)

Albert, Brice J.; Pahng, Seong Ho; Alaniva, Nicholas; Sesti, Erika L.; Rand, Peter W.; Saliba, Edward P.; Scott, Faith J.; Choi, Eric J.; Barnes, Alexander B.

2017-10-01

Cryogenic sample temperatures can enhance NMR sensitivity by extending spin relaxation times to improve dynamic nuclear polarization (DNP) and by increasing Boltzmann spin polarization. We have developed an efficient heat exchanger with a liquid nitrogen consumption rate of only 90 L per day to perform magic-angle spinning (MAS) DNP experiments below 85 K. In this heat exchanger implementation, cold exhaust gas from the NMR probe is returned to the outer portion of a counterflow coil within an intermediate cooling stage to improve cooling efficiency of the spinning and variable temperature gases. The heat exchange within the counterflow coil is calculated with computational fluid dynamics to optimize the heat transfer. Experimental results using the novel counterflow heat exchanger demonstrate MAS DNP signal enhancements of 328 ± 3 at 81 ± 2 K, and 276 ± 4 at 105 ± 2 K.

Aftershocks following crash of currency exchange rate: The case of RUB/USD in 2014

NASA Astrophysics Data System (ADS)

Usmanova, Vasilya; Lysogorskiy, Yury V.; Abe, Sumiyoshi

2018-02-01

The dynamical behavior of the currency exchange rate after its large-scale catastrophe is discussed through a case study of the rate of Russian rubles to US dollars after its crash in 2014. It is shown that, similarly to the case of the stock market crash, the relaxation is characterized by a power law, which is in analogy with the Omori-Utsu law for earthquake aftershocks. The waiting-time distribution is found to also obey a power law. Furthermore, the event-event correlation is discussed, and the aging phenomenon and scaling property are observed. Comments are made on (non-)Markovianity of the aftershock process and on a possible relevance of glassy dynamics to the market system after the crash.

Side-chain dynamics of a detergent-solubilized membrane protein: Measurement of tryptophan and glutamine hydrogen-exchange rates in M13 coat protein by sup 1 H NMR spectroscopy

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

O'Neil, J.D.J.; Sykes, B.D.

M13 coat protein is a small (50 amino acids) lipid-soluble protein that becomes an integral membrane protein during the infection stage of the life cycle of the M13 phage and is therefore used as a model membrane protein. To study side-chain dynamics in the protein, the authors have measured individual hydrogen-exchange rates for a primary amide in the side chain of glutamine-15 and for the indole amine of tryptophan-26. The protein was solubilized with the use of perdeuteriated sodium dodecyl sulfate (SDS), and hydrogen-exchange rates were measured by using {sup 1}H nuclear magnetic resonance spectroscopy. The glutamine-15 syn proton exchangedmore » at a rate identical with that in glutamine model peptides except that the pH corresponding to minimum exchange was elevated by about 1.5 pH units. The tryptophan-26 indole amine proton exchange was biphasic, suggesting that two populations of tryptophan-26 exist. It is suggested that the two populations may reflect protein dimerization or aggregation in the SDS micelles. The pH values of minimum exchange for tryptophan-26 in both environments were also elevated by 1.3-1.9 pH units. This phenomenon is reproduced when small tryptophan- and glutamine-containing hydrophobic peptides are dissolved in the presence of SDS micelles. The electrostatic nature of this phenomenon is proven by showing that the minimum pH for exchange can be reduced by dissolving the hydrophobic peptides in the positively charged detergent micelle dodecyltrimethylammonium bromide.« less

Time-series analysis of foreign exchange rates using time-dependent pattern entropy

NASA Astrophysics Data System (ADS)

Ishizaki, Ryuji; Inoue, Masayoshi

2013-08-01

Time-dependent pattern entropy is a method that reduces variations to binary symbolic dynamics and considers the pattern of symbols in a sliding temporal window. We use this method to analyze the instability of daily variations in foreign exchange rates, in particular, the dollar-yen rate. The time-dependent pattern entropy of the dollar-yen rate was found to be high in the following periods: before and after the turning points of the yen from strong to weak or from weak to strong, and the period after the Lehman shock.

A dynamic analysis of S&P 500, FTSE 100 and EURO STOXX 50 indices under different exchange rates

PubMed Central

Chen, Yanhua; Mantegna, Rosario N.; Zuev, Konstantin M.

2018-01-01

In this study, we assess the dynamic evolution of short-term correlation, long-term cointegration and Error Correction Model (hereafter referred to as ECM)-based long-term Granger causality between each pair of US, UK, and Eurozone stock markets from 1980 to 2015 using the rolling-window technique. A comparative analysis of pairwise dynamic integration and causality of stock markets, measured in common and domestic currency terms, is conducted to evaluate comprehensively how exchange rate fluctuations affect the time-varying integration among the S&P 500, FTSE 100 and EURO STOXX 50 indices. The results obtained show that the dynamic correlation, cointegration and ECM-based long-run Granger causality vary significantly over the whole sample period. The degree of dynamic correlation and cointegration between pairs of stock markets rises in periods of high volatility and uncertainty, especially under the influence of economic, financial and political shocks. Meanwhile, we observe the weaker and decreasing correlation and cointegration among the three developed stock markets during the recovery periods. Interestingly, the most persistent and significant cointegration among the three developed stock markets exists during the 2007–09 global financial crisis. Finally, the exchange rate fluctuations, also influence the dynamic integration and causality between all pairs of stock indices, with that influence increasing under the local currency terms. Our results suggest that the potential for diversifying risk by investing in the US, UK and Eurozone stock markets is limited during the periods of economic, financial and political shocks. PMID:29529092

Determination of glucose exchange rates and permeability of erythrocyte membrane in preeclampsia and subsequent oxidative stress-related protein damage using dynamic-19F-NMR.

PubMed

Dickinson, Elizabeth; Arnold, John R P; Fisher, Julie

2017-02-01

The cause of the pregnancy condition preeclampsia (PE) is thought to be endothelial dysfunction caused by oxidative stress. As abnormal glucose tolerance has also been associated with PE, we use a fluorinated-mimic of this metabolite to establish whether any oxidative damage to lipids and proteins in the erythrocyte membrane has increased cell membrane permeability. Data were acquired using 19 F Dynamic-NMR (DNMR) to measure exchange of 3-fluoro-3-deoxyglucose (3-FDG) across the membrane of erythrocytes from 10 pregnant women (5 healthy control women, and 5 from women suffering from PE). Magnetisation transfer was measured using the 1D selective inversion and 2D EXSY pulse sequences, over a range of time delays. Integrated intensities from these experiments were used in matrix diagonalisation to estimate the values of the rate constants of exchange and membrane permeability. No significant differences were observed for the rate of exchange of 3-FDG and membrane permeability between healthy pregnant women and those suffering from PE, leading us to conclude that no oxidative damage had occurred at this carrier-protein site in the membrane.

Investigation of Anion-Exchange and Immunoaffinity Particle-Loaded Membranes for the Isolation of Charged Organic Analytes from Water

USGS Publications Warehouse

Dombrowski, T.R.; Wilson, G.S.; Thurman, E.M.

1998-01-01

Anion-exchange and immunoaffinity particle loaded membranes (PLMs) were investigated as a mechanism for the isolation of charged organic analytes from water. Kinetic properties determined theoretically included dynamic capacity, pressure drop (??P), residence and diffusion times (Tr, Td), and total membrane porosity (???T). These properties were confirmed through experimental evaluation, and the PLM method showed significant improvement over conventional solid-phase extraction (SPE) and ion-exchange formats. Recoveries of more than 90% were observed for a variety of test compounds at flow rates up to 70 mL/min (equipment-limited maximum flow rate). A fast-flow immunoaffinity column was developed using antibodies (Abs) attached to the PLMs. Reproducible recoveries (88% ?? 4%) were observed at flow rates up to 70 mL/min for the antibody (Ab)-loaded PLMs. Findings indicate increased selectivity over anion-exchange PLMs and conventional SPE or ion-exchange methods and rapid Ab-antigen binding rates given the excellent mass-transfer characteristics of the PLMs.

Spin polarization transfer by the radical pair mechanism

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

Zarea, Mehdi, E-mail: m-zarea@northwestern.edu; Ratner, Mark A.; Wasielewski, Michael R.

2015-08-07

In a three-site representation, we study a spin polarization transfer from radical pair spins to a nearby electron or nuclear spin. The quantum dynamics of the radical pair spins is governed by a constant exchange interaction between the radical pair spins which have different Zeeman frequencies. Radical pair spins can recombine to the singlet ground state or to lower energy triplet states. It is then shown that the coherent dynamics of the radical pair induces spin polarization on the nearby third spin in the presence of a magnetic field. The spin polarization transfer depends on the difference between Zeeman frequencies,more » the singlet and triplet recombination rates, and on the exchange and dipole-dipole interactions between the different spins. In particular, the sign of the polarization depends on the exchange coupling between radical pair spins and also on the difference between singlet and triplet recombination rate constants.« less

Hydrogen and methanol exchange processes for (TMP)Rh-OCH3(CH3OH) in binary solutions of methanol and benzene.

PubMed

Sarkar, Sounak; Li, Shan; Wayland, Bradford B

2011-04-18

Tetramesityl porphinato rhodium(III) methoxide ((TMP)Rh-OCH(3)) binds with methanol in benzene to form a 1:1 methanol complex ((TMP)Rh-OCH(3)(CH(3)OH)) (1). Dynamic processes are observed to occur for the rhodium(III) methoxide methanol complex (1) that involve both hydrogen and methanol exchange. Hydrogen exchange between coordinated methanol and methoxide through methanol in solution results in an interchange of the environments for the non-equivalent porphyrin faces that contain methoxide and methanol ligands. Interchange of the environments of the coordinated methanol and methoxide sites in 1 produces interchange of the inequivalent mesityl o-CH(3) groups, but methanol ligand exchange occurs on one face of the porphyrin and the mesityl o-CH(3) groups remain inequivalent. Rate constants for dynamic processes are evaluated by full line shape analysis for the (1)H NMR of the mesityl o-CH(3) and high field methyl resonances of coordinated methanol and methoxide groups in 1. The rate constant for interchange of the inequivalent porphyrin faces is associated with hydrogen exchange between 1 and methanol in solution and is observed to increase regularly with the increase in the mole fraction of methanol. The rate constant for methanol ligand exchange between 1 and the solution varies with the solution composition and fluctuates in a manner that parallels the change in the activation energy for methanol diffusion which is a consequence of solution non-ideality from hydrogen bonded clusters.

Comparison of two adaptive temperature-based replica exchange methods applied to a sharp phase transition of protein unfolding-folding.

PubMed

Lee, Michael S; Olson, Mark A

2011-06-28

Temperature-based replica exchange (T-ReX) enhances sampling of molecular dynamics simulations by autonomously heating and cooling simulation clients via a Metropolis exchange criterion. A pathological case for T-ReX can occur when a change in state (e.g., folding to unfolding of a protein) has a large energetic difference over a short temperature interval leading to insufficient exchanges amongst replica clients near the transition temperature. One solution is to allow the temperature set to dynamically adapt in the temperature space, thereby enriching the population of clients near the transition temperature. In this work, we evaluated two approaches for adapting the temperature set: a method that equalizes exchange rates over all neighbor temperature pairs and a method that attempts to induce clients to visit all temperatures (dubbed "current maximization") by positioning many clients at or near the transition temperature. As a test case, we simulated the 57-residue SH3 domain of alpha-spectrin. Exchange rate equalization yielded the same unfolding-folding transition temperature as fixed-temperature ReX with much smoother convergence of this value. Surprisingly, the current maximization method yielded a significantly lower transition temperature, in close agreement with experimental observation, likely due to more extensive sampling of the transition state.

Merging constitutional and motional covalent dynamics in reversible imine formation and exchange processes.

PubMed

Kovaříček, Petr; Lehn, Jean-Marie

2012-06-06

The formation and exchange processes of imines of salicylaldehyde, pyridine-2-carboxaldehyde, and benzaldehyde have been studied, showing that the former has features of particular interest for dynamic covalent chemistry, displaying high efficiency and fast rates. The monoimines formed with aliphatic α,ω-diamines display an internal exchange process of self-transimination type, inducing a local motion of either "stepping-in-place" or "single-step" type by bond interchange, whose rate decreases rapidly with the distance of the terminal amino groups. Control of the speed of the process over a wide range may be achieved by substituents, solvent composition, and temperature. These monoimines also undergo intermolecular exchange, thus merging motional and constitutional covalent behavior within the same molecule. With polyamines, the monoimines formed execute internal motions that have been characterized by extensive one-dimensional, two-dimensional, and EXSY proton NMR studies. In particular, with linear polyamines, nondirectional displacement occurs by shifting of the aldehyde residue along the polyamine chain serving as molecular track. Imines thus behave as simple prototypes of systems displaying relative motions of molecular moieties, a subject of high current interest in the investigation of synthetic and biological molecular motors. The motional processes described are of dynamic covalent nature and take place without change in molecular constitution. They thus represent a category of dynamic covalent motions, resulting from reversible covalent bond formation and dissociation. They extend dynamic covalent chemistry into the area of molecular motions. A major further step will be to achieve control of directionality. The results reported here for imines open wide perspectives, together with other chemical groups, for the implementation of such features in multifunctional molecules toward the design of molecular devices presenting a complex combination of motional and constitutional dynamic behaviors.

Oxygen ionization rates at Mars and Venus - Relative contributions of impact ionization and charge exchange

NASA Astrophysics Data System (ADS)

Zhang, M. H. G.; Luhmann, J. G.; Nagy, A. F.; Spreiter, J. R.; Stahara, S. S.

1993-02-01

Oxygen ion production rates above the ionopauses of Venus and Mars are calculated for photoionization, charge exchange, and solar wind electron impact ionization processes. The latter two require the use of the Spreiter and Stahara (1980) gas dynamic model to estimate magnetosheath velocities, densities, and temperatures. The results indicate that impact ionization is the dominant mechanism for the production of O(+) ions at both Venus and Mars. This finding might explain both the high ion escape rates measured by Phobos 2 and the greater mass loading rate inferred for Venus from the bow shock positions.

Correlation between Gini index and mobility in a stochastic kinetic model of economic exchange

NASA Astrophysics Data System (ADS)

Bertotti, Maria Letizia; Chattopadhyay, Amit K.; Modanese, Giovanni

Starting from a class of stochastically driven kinetic models of economic exchange, here we present results highlighting the correlation of the Gini inequality index with the social mobility rate, close to dynamical equilibrium. Except for the "canonical-additive case", our numerical results consistently indicate negative values of the correlation coefficient, in agreement with empirical evidence. This confirms that growing inequality is not conducive to social mobility which then requires an "external source" to sustain its dynamics. On the other hand, the sign of the correlation between inequality and total income in the canonical ensemble depends on the way wealth enters or leaves the system. At a technical level, the approach involves a generalization of a stochastic dynamical system formulation, that further paves the way for a probabilistic formulation of perturbed economic exchange models.

Modelling on optimal portfolio with exchange rate based on discontinuous stochastic process

NASA Astrophysics Data System (ADS)

Yan, Wei; Chang, Yuwen

2016-12-01

Considering the stochastic exchange rate, this paper is concerned with the dynamic portfolio selection in financial market. The optimal investment problem is formulated as a continuous-time mathematical model under mean-variance criterion. These processes follow jump-diffusion processes (Weiner process and Poisson process). Then the corresponding Hamilton-Jacobi-Bellman(HJB) equation of the problem is presented and its efferent frontier is obtained. Moreover, the optimal strategy is also derived under safety-first criterion.

Empirical Correction for Differences in Chemical Exchange Rates in Hydrogen Exchange-Mass Spectrometry Measurements.

PubMed

Toth, Ronald T; Mills, Brittney J; Joshi, Sangeeta B; Esfandiary, Reza; Bishop, Steven M; Middaugh, C Russell; Volkin, David B; Weis, David D

2017-09-05

A barrier to the use of hydrogen exchange-mass spectrometry (HX-MS) in many contexts, especially analytical characterization of various protein therapeutic candidates, is that differences in temperature, pH, ionic strength, buffering agent, or other additives can alter chemical exchange rates, making HX data gathered under differing solution conditions difficult to compare. Here, we present data demonstrating that HX chemical exchange rates can be substantially altered not only by the well-established variables of temperature and pH but also by additives including arginine, guanidine, methionine, and thiocyanate. To compensate for these additive effects, we have developed an empirical method to correct the hydrogen-exchange data for these differences. First, differences in chemical exchange rates are measured by use of an unstructured reporter peptide, YPI. An empirical chemical exchange correction factor, determined by use of the HX data from the reporter peptide, is then applied to the HX measurements obtained from a protein of interest under different solution conditions. We demonstrate that the correction is experimentally sound through simulation and in a proof-of-concept experiment using unstructured peptides under slow-exchange conditions (pD 4.5 at ambient temperature). To illustrate its utility, we applied the correction to HX-MS excipient screening data collected for a pharmaceutically relevant IgG4 mAb being characterized to determine the effects of different formulations on backbone dynamics.

One- and two-dimensional chemical exchange nuclear magnetic resonance studies of the creatine kinase catalyzed reaction

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

Gober, J.R.

1988-01-01

The equilibrium chemical exchange dynamics of the creatine kinase enzyme system were studied by one- and two-dimensional {sup 31}P NMR techniques. Pseudo-first-order reaction rate constants were measured by the saturation transfer method under an array of experimental conditions of pH and temperature. Quantitative one-dimensional spectra were collected under the same conditions in order to calculate the forward and reverse reaction rates, the K{sub eq}, the hydrogen ion stoichiometry, and the standard thermodynamic functions. The pure absorption mode in four quadrant two-dimensional chemical exchange experiment was employed so that the complete kinetic matrix showing all of the chemical exchange process couldmore » be realized.« less

Utilizing multichannel electrical resistivity methods to examine the dynamics of the fresh water–seawater interface in two Hawaiian groundwater systems

USGS Publications Warehouse

Dimova, Natasha T.; Swarzenski, Peter W.; Dulaiova, Henrieta; Glenn, Craig R.

2012-01-01

Multichannel electrical resistivity (ER) measurements were conducted at two contrasting coastal sites in Hawaii to obtain new information on the spatial scales and dynamics of the fresh water–seawater interface and rates of coastal groundwater exchange. At Kiholo Bay (located on the dry, Kona side of the Big Island) and at a site in Maunalua Bay (Oahu), there is an evidence for abundant submarine groundwater discharge (SGD). However, the hydrologic and geologic controls on coastal groundwater discharge are likely to be different at these two sites. While at Kiholo Bay SGD is predominantly through lava tubes, at the Maunalua Bay site exchange occurs mostly through nearshore submarine springs. In order to calculate SGD fluxes, it is important to understand the spatial and temporal scales of coastal groundwater exchange. From ER time series data, subsurface salinity distributions were calculated using site-specific formation factors. A salinity mass balance box model was then used to calculate rates of point source (i.e., spatially discreet) and total fresh water discharge. From these data, mean SGD rates were calculated for Kiholo Bay (∼9,200 m3/d) and for the Maunalua Bay site (∼5,900 m3/d). While such results are on the same order of magnitude to geochemical tracer-derived SGD rates, the ER SGD rates provide enhanced details of coastal groundwater exchange that can enable a more cohesive whole watershed perspective.

Communication: Rigorous quantum dynamics of O + O{sub 2} exchange reactions on an ab initio potential energy surface substantiate the negative temperature dependence of rate coefficients

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

Li, Yaqin; Sun, Zhigang, E-mail: zsun@dicp.ac.cn, E-mail: dawesr@mst.edu, E-mail: hguo@unm.edu; Center for Advanced Chemical Physics, University of Science and Technology of China, 96 Jinzhai Road, Hefei 230026

2014-08-28

The kinetics and dynamics of several O + O{sub 2} isotope exchange reactions have been investigated on a recently determined accurate global O{sub 3} potential energy surface using a time-dependent wave packet method. The agreement between calculated and measured rate coefficients is significantly improved over previous work. More importantly, the experimentally observed negative temperature dependence of the rate coefficients is for the first time rigorously reproduced theoretically. This negative temperature dependence can be attributed to the absence in the new potential energy surface of a submerged “reef” structure, which was present in all previous potential energy surfaces. In addition, contributionsmore » of rotational excited states of the diatomic reactant further accentuate the negative temperature dependence.« less

Ras activation by SOS: Allosteric regulation by altered fluctuation dynamics

PubMed Central

Iversen, Lars; Tu, Hsiung-Lin; Lin, Wan-Chen; Christensen, Sune M.; Abel, Steven M.; Iwig, Jeff; Wu, Hung-Jen; Gureasko, Jodi; Rhodes, Christopher; Petit, Rebecca S.; Hansen, Scott D.; Thill, Peter; Yu, Cheng-Han; Stamou, Dimitrios; Chakraborty, Arup K.; Kuriyan, John; Groves, Jay T.

2014-01-01

Activation of the small guanosine triphosphatase H-Ras by the exchange factor Son of Sevenless (SOS) is an important hub for signal transduction. Multiple layers of regulation, through protein and membrane interactions, govern activity of SOS. We characterized the specific activity of individual SOS molecules catalyzing nucleotide exchange in H-Ras. Single-molecule kinetic traces revealed that SOS samples a broad distribution of turnover rates through stochastic fluctuations between distinct, long-lived (more than 100 seconds), functional states. The expected allosteric activation of SOS by Ras–guanosine triphosphate (GTP) was conspicuously absent in the mean rate. However, fluctuations into highly active states were modulated by Ras-GTP. This reveals a mechanism in which functional output may be determined by the dynamical spectrum of rates sampled by a small number of enzymes, rather than the ensemble average. PMID:24994643

Double proton transfer in the complex of acetic acid with methanol: Theory versus experiment

NASA Astrophysics Data System (ADS)

Fernández-Ramos, Antonio; Smedarchina, Zorka; Rodríguez-Otero, Jesús

2001-01-01

To test the approximate instanton approach to intermolecular proton-transfer dynamics, we report multidimensional ab initio bimolecular rate constants of HH, HD, and DD exchange in the complex of acetic acid with methanol in tetrahydrofuran-d8, and compare them with the NMR (nuclear magnetic resonance) experiments of Gerritzen and Limbach. The bimolecular rate constants are evaluated as products of the exchange rates and the equilibrium rate constants of complex formation in solution. The two molecules form hydrogen-bond bridges and the exchange occurs via concerted transfer of two protons. The dynamics of this transfer is evaluated in the complete space of 36 vibrational degrees of freedom. The geometries of the two isolated molecules, the complex, and the transition states corresponding to double proton transfer are fully optimized at QCISD (quadratic configuration interaction including single and double substitutions) level of theory, and the normal-mode frequencies are calculated at MP2 (Møller-Plesset perturbation theory of second order) level with the 6-31G (d,p) basis set. The presence of the solvent is taken into account via single-point calculations over the gas phase geometries with the PCM (polarized continuum model). The proton exchange rate constants, calculated with the instanton method, show the effect of the structure and strength of the hydrogen bonds, reflected in the coupling between the tunneling motion and the other vibrations of the complex. Comparison with experiment, which shows substantial kinetic isotopic effects (KIE), indicates that tunneling prevails over classic exchange for the whole temperature range of observation. The unusual behavior of the experimental KIE upon single and double deuterium substitution is well reproduced and is related to the synchronicity of two-atom tunneling.

Mutual Information Rate and Bounds for It

PubMed Central

Baptista, Murilo S.; Rubinger, Rero M.; Viana, Emilson R.; Sartorelli, José C.; Parlitz, Ulrich; Grebogi, Celso

2012-01-01

The amount of information exchanged per unit of time between two nodes in a dynamical network or between two data sets is a powerful concept for analysing complex systems. This quantity, known as the mutual information rate (MIR), is calculated from the mutual information, which is rigorously defined only for random systems. Moreover, the definition of mutual information is based on probabilities of significant events. This work offers a simple alternative way to calculate the MIR in dynamical (deterministic) networks or between two time series (not fully deterministic), and to calculate its upper and lower bounds without having to calculate probabilities, but rather in terms of well known and well defined quantities in dynamical systems. As possible applications of our bounds, we study the relationship between synchronisation and the exchange of information in a system of two coupled maps and in experimental networks of coupled oscillators. PMID:23112809

USSR Report, World Economy and International Relations, No. 10, October 1986

DTIC Science & Technology

1987-01-15

for international comparative studies, for prognosis of exchange rates dynamics. The exchange rates formation gains special attention in the article...traditional bourgeois " models " like the classical 19th century "balance of power". We would recall merely H. Kissinger’s book "A World Restored," which...1980’s the average per capita income level here was 11 times lower than in the developed capitalist countries. And thoughout the past three decades

Correlation structures in short-term variabilities of stock indices and exchange rates

NASA Astrophysics Data System (ADS)

Nakamura, Tomomichi; Small, Michael

2007-09-01

Financial data usually show irregular fluctuations and some trends. We investigate whether there are correlation structures in short-term variabilities (irregular fluctuations) among financial data from the viewpoint of deterministic dynamical systems. Our method is based on the small-shuffle surrogate method. The data we use are daily closing price of Standard & Poor's 500 and the volume, and daily foreign exchange rates, Euro/US Dollar (USD), British Pound/USD and Japanese Yen/USD. We found that these data are not independent.

Estimating long-run equilibrium real exchange rates: short-lived shocks with long-lived impacts on Pakistan.

PubMed

Zardad, Asma; Mohsin, Asma; Zaman, Khalid

2013-12-01

The purpose of this study is to investigate the factors that affect real exchange rate volatility for Pakistan through the co-integration and error correction model over a 30-year time period, i.e. between 1980 and 2010. The study employed the autoregressive conditional heteroskedasticity (ARCH), generalized autoregressive conditional heteroskedasticity (GARCH) and Vector Error Correction model (VECM) to estimate the changes in the volatility of real exchange rate series, while an error correction model was used to determine the short-run dynamics of the system. The study is limited to a few variables i.e., productivity differential (i.e., real GDP per capita relative to main trading partner); terms of trade; trade openness and government expenditures in order to manage robust data. The result indicates that real effective exchange rate (REER) has been volatile around its equilibrium level; while, the speed of adjustment is relatively slow. VECM results confirm long run convergence of real exchange rate towards its equilibrium level. Results from ARCH and GARCH estimation shows that real shocks volatility persists, so that shocks die out rather slowly, and lasting misalignment seems to have occurred.

Proceedings of the NITINOL Heat Engine Conference, 26-27 September 1978, Silver Spring, Maryland

DTIC Science & Technology

1978-09-27

allowed us to design, build, and test various engine designs, while exploring advanced concepts with computer modeling of motor dynamics and heat exchange ...exclude the effects of element geometi y and other material parameters which affect the heat exchange rate and kinetics of the SRP. 5-3...is in Rference 8. 13. In the present work we exclude the effects of element geometry and other material parameters which affect the heat exchange

Power-law behaviour evaluation from foreign exchange market data using a wavelet transform method

NASA Astrophysics Data System (ADS)

Wei, H. L.; Billings, S. A.

2009-09-01

Numerous studies in the literature have shown that the dynamics of many time series including observations in foreign exchange markets exhibit scaling behaviours. A simple new statistical approach, derived from the concept of the continuous wavelet transform correlation function (WTCF), is proposed for the evaluation of power-law properties from observed data. The new method reveals that foreign exchange rates obey power-laws and thus belong to the class of self-similarity processes.

Comparison of SH3 and SH2 domain dynamics when expressed alone or in an SH(3+2) construct: the role of protein dynamics in functional regulation.

PubMed

Engen, J R; Smithgall, T E; Gmeiner, W H; Smith, D L

1999-04-02

Protein dynamics play an important role in protein function and regulation of enzymatic activity. To determine how additional interactions with surrounding structure affects local protein dynamics, we have used hydrogen exchange and mass spectrometry to investigate the SH2 and SH3 domains of the protein tyrosine kinase Hck. Exchange rates of isolated Hck SH3 and SH2 domains were compared with rates for the same domains when part of a larger SH(3+2) construct. Increased deuterium incorporation was observed for the SH3 domain in the joint construct, particularly near the SH2 interface and the short sequence that connects SH3 to SH2, implying greater flexibility of SH3 when it is part of SH(3+2). Slow cooperative unfolding of the SH3 domain occurred at the same rate in isolated SH3 as in the SH(3+2) construct, suggesting a functional significance for this unfolding. The SH2 domain displayed relatively smaller changes in flexibility when part of the SH(3+2) construct. These results suggest that the domains influence each other. Further, our results imply a link between functional regulation and structural dynamics of SH3 and SH2 domains. Copyright 1999 Academic Press.

Precise determination of water exchanges on a mineral surface

DOE PAGES

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

2016-10-03

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

Molecular kinetics. Ras activation by SOS: allosteric regulation by altered fluctuation dynamics.

PubMed

Iversen, Lars; Tu, Hsiung-Lin; Lin, Wan-Chen; Christensen, Sune M; Abel, Steven M; Iwig, Jeff; Wu, Hung-Jen; Gureasko, Jodi; Rhodes, Christopher; Petit, Rebecca S; Hansen, Scott D; Thill, Peter; Yu, Cheng-Han; Stamou, Dimitrios; Chakraborty, Arup K; Kuriyan, John; Groves, Jay T

2014-07-04

Activation of the small guanosine triphosphatase H-Ras by the exchange factor Son of Sevenless (SOS) is an important hub for signal transduction. Multiple layers of regulation, through protein and membrane interactions, govern activity of SOS. We characterized the specific activity of individual SOS molecules catalyzing nucleotide exchange in H-Ras. Single-molecule kinetic traces revealed that SOS samples a broad distribution of turnover rates through stochastic fluctuations between distinct, long-lived (more than 100 seconds), functional states. The expected allosteric activation of SOS by Ras-guanosine triphosphate (GTP) was conspicuously absent in the mean rate. However, fluctuations into highly active states were modulated by Ras-GTP. This reveals a mechanism in which functional output may be determined by the dynamical spectrum of rates sampled by a small number of enzymes, rather than the ensemble average. Copyright © 2014, American Association for the Advancement of Science.

Control of Advanced Reactor-Coupled Heat Exchanger System: Incorporation of Reactor Dynamics in System Response to Load Disturbances

DOE PAGES

Skavdahl, Isaac; Utgikar, Vivek; Christensen, Richard; ...

2016-05-24

We present an alternative control schemes for an Advanced High Temperature Reactor system consisting of a reactor, an intermediate heat exchanger, and a secondary heat exchanger (SHX) in this paper. One scheme is designed to control the cold outlet temperature of the SHX (T co) and the hot outlet temperature of the intermediate heat exchanger (T ho2) by manipulating the hot-side flow rates of the heat exchangers (F h/F h2) responding to the flow rate and temperature disturbances. The flow rate disturbances typically require a larger manipulation of the flow rates than temperature disturbances. An alternate strategy examines the controlmore » of the cold outlet temperature of the SHX (T co) only, since this temperature provides the driving force for energy production in the power conversion unit or the process application. The control can be achieved by three options: (1) flow rate manipulation; (2) reactor power manipulation; or (3) a combination of the two. The first option has a quicker response but requires a large flow rate change. The second option is the slowest but does not involve any change in the flow rates of streams. The final option appears preferable as it has an intermediate response time and requires only a minimal flow rate change.« less

Super-resolution microscopy reveals structural diversity in molecular exchange among peptide amphiphile nanofibres

DOE PAGES

da Silva, Ricardo M. P.; van der Zwaag, Daan; Albertazzi, Lorenzo; ...

2016-05-19

The dynamic behaviour of supramolecular systems is an important dimension of their potential functions. Here, we report on the use of stochastic optical reconstruction microscopy to study the molecular exchange of peptide amphiphile nanofibres, supramolecular systems known to have important biomedical functions. Solutions of nanofibres labelled with different dyes (Cy3 and Cy5) were mixed, and the distribution of dyes inserting into initially single-colour nanofibres was quantified using correlative image analysis. Our observations are consistent with an exchange mechanism involving monomers or small clusters of molecules inserting randomly into a fibre. Different exchange rates are observed within the same fibre, suggestingmore » that local cohesive structures exist on the basis of beta-sheet discontinuous domains. The results reported here show that peptide amphiphile supramolecular systems can be dynamic and that their intermolecular interactions affect exchange patterns. Lastly, this information can be used to generate useful aggregate morphologies for improved biomedical function.« less

Acidity and hydrogen exchange dynamics of iron(II)-bound nitroxyl in aqueous solution.

PubMed

Gao, Yin; Toubaei, Abouzar; Kong, Xianqi; Wu, Gang

2014-10-20

Nitroxyl-iron(II) (HNO-Fe(II)) complexes are often unstable in aqueous solution, thus making them very difficult to study. Consequently, many fundamental chemical properties of Fe(II)-bound HNO have remained unknown. Using a comprehensive multinuclear ((1)H, (15)N, (17)O) NMR approach, the acidity of the Fe(II)-bound HNO in [Fe(CN)5(HNO)](3-) was investigated and its pK(a) value was determined to be greater than 11. Additionally, HNO undergoes rapid hydrogen exchange with water in aqueous solution and this exchange process is catalyzed by both acid and base. The hydrogen exchange dynamics for the Fe(II)-bound HNO have been characterized and the obtained benchmark values, when combined with the literature data on proteins, reveal that the rate of hydrogen exchange for the Fe(II)-bound HNO in the interior of globin proteins is reduced by a factor of 10(6). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Dang, Liem X.; Vo, Quynh N.; Nilsson, Mikael

We report one of the first simulations using a classical rate theory approach to predict the mechanism of the exchange process between water and aqueous uranyl ions. Using our water and ion-water polarizable force fields and molecular dynamics techniques, we computed the potentials of mean force for the uranyl ion-water pair as the function of pressures at ambient temperature. Subsequently, these simulated potentials of mean force were used to calculate rate constants using the transition rate theory; the time dependent transmission coefficients were also examined using the reactive flux method and Grote-Hynes treatments of the dynamic response of the solvent.more » The computed activation volumes using transition rate theory and the corrected rate constants are positive, thus the mechanism of this particular water-exchange is a dissociative process. We discuss our rate theory results and compare them with previously studies in which non-polarizable force fields were used. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.« less

Carbon dioxide exchange rates from short- and long-hydroperiod Everglades freshwater marsh

Treesearch

K. L. Jimenez; G. Starr; C. L. Staudhammer; J. L. Schedlbauer; H. W. Loescher; Sparkle L Malone; S. F. Oberbauer

2012-01-01

Everglades freshwater marshes were once carbon sinks, but human-driven hydrologic changes have led to uncertainty about the current state of their carbon dynamics. To investigate the effect of hydrology on CO2 exchange, we used eddy covariance measurements for 2 years (2008-2009) in marl (short-hydroperiod) and peat (long-hydroperiod) wetlands in Everglades National...

Coupling of phytoplankton uptake and air-water exchange of persistent organic pollutants

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

Dachs, J.; Eisenreich, S.J.; Baker, J.E.

1999-10-15

A dynamic model that couples air-water exchange and phytoplankton uptake of persistent organic pollutants has been developed and then applied to PCB data from a small experimental lake. A sensitivity analysis of the model, taking into account the influence of physical environmental conditions such as temperature, wind speed, and mixing depth as well as plankton-related parameters such as biomass and growth rate was carried out for a number of PCBs with different physical-chemical properties. The results indicate that air-water exchange dynamics are influenced not only by physical parameters but also by phytoplankton biomass and growth rate. New phytoplankton production resultsmore » in substantially longer times to reach equilibrium. Phytoplankton uptake-induced depletion of the dissolved phase concentration maintains air and water phases out of equilibrium. Furthermore, PCBs in phytoplankton also take longer times to reach equilibrium with the dissolved water phase when the latter is supported by diffusive air-water exchange. However, both model analysis and model application to the Experimental Lakes Area of northwestern Ontario (Canada) suggest that the gas phase supports the concentrations of persistent organic pollutants, such as PCBs, in atmospherically driven aquatic environments.« less

Validation of a Multimodality Flow Phantom and Its Application for Assessment of Dynamic SPECT and PET Technologies.

PubMed

Gabrani-Juma, Hanif; Clarkin, Owen J; Pourmoghaddas, Amir; Driscoll, Brandon; Wells, R Glenn; deKemp, Robert A; Klein, Ran

2017-01-01

Simple and robust techniques are lacking to assess performance of flow quantification using dynamic imaging. We therefore developed a method to qualify flow quantification technologies using a physical compartment exchange phantom and image analysis tool. We validate and demonstrate utility of this method using dynamic PET and SPECT. Dynamic image sequences were acquired on two PET/CT and a cardiac dedicated SPECT (with and without attenuation and scatter corrections) systems. A two-compartment exchange model was fit to image derived time-activity curves to quantify flow rates. Flowmeter measured flow rates (20-300 mL/min) were set prior to imaging and were used as reference truth to which image derived flow rates were compared. Both PET cameras had excellent agreement with truth ( [Formula: see text]). High-end PET had no significant bias (p > 0.05) while lower-end PET had minimal slope bias (wash-in and wash-out slopes were 1.02 and 1.01) but no significant reduction in precision relative to high-end PET (<15% vs. <14% limits of agreement, p > 0.3). SPECT (without scatter and attenuation corrections) slope biases were noted (0.85 and 1.32) and attributed to camera saturation in early time frames. Analysis of wash-out rates from non-saturated, late time frames resulted in excellent agreement with truth ( [Formula: see text], slope = 0.97). Attenuation and scatter corrections did not significantly impact SPECT performance. The proposed phantom, software and quality assurance paradigm can be used to qualify imaging instrumentation and protocols for quantification of kinetic rate parameters using dynamic imaging.

Hydrogen exchange mass spectrometry of functional membrane-bound chemotaxis receptor complexes.

PubMed

Koshy, Seena S; Eyles, Stephen J; Weis, Robert M; Thompson, Lynmarie K

2013-12-10

The transmembrane signaling mechanism of bacterial chemotaxis receptors is thought to involve changes in receptor conformation and dynamics. The receptors function in ternary complexes with two other proteins, CheA and CheW, that form extended membrane-bound arrays. Previous studies have shown that attractant binding induces a small (∼2 Å) piston displacement of one helix of the periplasmic and transmembrane domains toward the cytoplasm, but it is not clear how this signal propagates through the cytoplasmic domain to control the kinase activity of the CheA bound at the membrane-distal tip, nearly 200 Å away. The cytoplasmic domain has been shown to be highly dynamic, which raises the question of how a small piston motion could propagate through a dynamic domain to control CheA kinase activity. To address this, we have developed a method for measuring dynamics of the receptor cytoplasmic fragment (CF) in functional complexes with CheA and CheW. Hydrogen-deuterium exchange mass spectrometry (HDX-MS) measurements of global exchange of the CF demonstrate that the CF exhibits significantly slower exchange in functional complexes than in solution. Because the exchange rates in functional complexes are comparable to those of other proteins with similar structures, the CF appears to be a well-structured protein within these complexes, which is compatible with its role in propagating a signal that appears to be a tiny conformational change in the periplasmic and transmembrane domains of the receptor. We also demonstrate the feasibility of this protocol for local exchange measurements by incorporating a pepsin digest step to produce peptides with 87% sequence coverage and only 20% back exchange. This method extends HDX-MS to membrane-bound functional complexes without detergents that may perturb the stability or structure of the system.

Hydrogen Exchange Mass Spectrometry of Functional Membrane-bound Chemotaxis Receptor Complexes

PubMed Central

Koshy, Seena S.; Eyles, Stephen J.; Weis, Robert M.; Thompson, Lynmarie K.

2014-01-01

The transmembrane signaling mechanism of bacterial chemotaxis receptors is thought to involve changes in receptor conformation and dynamics. The receptors function in ternary complexes with two other proteins, CheA and CheW, that form extended membrane-bound arrays. Previous studies have shown that attractant binding induces a small (~2 Å) piston displacement of one helix of the periplasmic and transmembrane domains towards the cytoplasm, but it is not clear how this signal propagates through the cytoplasmic domain to control the kinase activity of the CheA bound at the membrane-distal tip, nearly 200 Å away. The cytoplasmic domain has been shown to be highly dynamic, which raises the question of how a small piston motion could propagate through a dynamic domain to control CheA kinase activity. To address this, we have developed a method for measuring dynamics of the receptor cytoplasmic fragment (CF) in functional complexes with CheA and CheW. Hydrogen exchange mass spectrometry (HDX-MS) measurements of global exchange of CF demonstrate that CF exhibits significantly slower exchange in functional complexes than in solution. Since the exchange rates in functional complexes are comparable to that of other proteins of similar structure, the CF appears to be a well-structured protein within these complexes, which is compatible with its role in propagating a signal that appears to be a tiny conformational change in the periplasmic and transmembrane domains of the receptor. We also demonstrate the feasibility of this protocol for local exchange measurements, by incorporating a pepsin digest step to produce peptides with 87% sequence coverage and only 20% back exchange. This method extends HDX-MS to membrane-bound functional complexes without detergents that may perturb the stability or structure of the system. PMID:24274333

What shakes the FX tree? Understanding currency dominance, dependence, and dynamics (Keynote Address)

NASA Astrophysics Data System (ADS)

Johnson, Neil F.; McDonald, Mark; Suleman, Omer; Williams, Stacy; Howison, Sam

2005-05-01

There is intense interest in understanding the stochastic and dynamical properties of the global Foreign Exchange (FX) market, whose daily transactions exceed one trillion US dollars. This is a formidable task since the FX market is characterized by a web of fluctuating exchange rates, with subtle inter-dependencies which may change in time. In practice, traders talk of particular currencies being 'in play' during a particular period of time -- yet there is no established machinery for detecting such important information. Here we apply the construction of Minimum Spanning Trees (MSTs) to the FX market, and show that the MST can capture important features of the global FX dynamics. Moreover, we show that the MST can help identify momentarily dominant and dependent currencies.

Allometric scaling law in a simple oxygen exchanging network: possible implications on the biological allometric scaling laws.

PubMed

Santillán, Moisés

2003-07-21

A simple model of an oxygen exchanging network is presented and studied. This network's task is to transfer a given oxygen rate from a source to an oxygen consuming system. It consists of a pipeline, that interconnects the oxygen consuming system and the reservoir and of a fluid, the active oxygen transporting element, moving through the pipeline. The network optimal design (total pipeline surface) and dynamics (volumetric flow of the oxygen transporting fluid), which minimize the energy rate expended in moving the fluid, are calculated in terms of the oxygen exchange rate, the pipeline length, and the pipeline cross-section. After the oxygen exchanging network is optimized, the energy converting system is shown to satisfy a 3/4-like allometric scaling law, based upon the assumption that its performance regime is scale invariant as well as on some feasible geometric scaling assumptions. Finally, the possible implications of this result on the allometric scaling properties observed elsewhere in living beings are discussed.

Dependence and risk assessment for oil prices and exchange rate portfolios: A wavelet based approach

NASA Astrophysics Data System (ADS)

Aloui, Chaker; Jammazi, Rania

2015-10-01

In this article, we propose a wavelet-based approach to accommodate the stylized facts and complex structure of financial data, caused by frequent and abrupt changes of markets and noises. Specifically, we show how the combination of both continuous and discrete wavelet transforms with traditional financial models helps improve portfolio's market risk assessment. In the empirical stage, three wavelet-based models (wavelet-EGARCH with dynamic conditional correlations, wavelet-copula, and wavelet-extreme value) are considered and applied to crude oil price and US dollar exchange rate data. Our findings show that the wavelet-based approach provides an effective and powerful tool for detecting extreme moments and improving the accuracy of VaR and Expected Shortfall estimates of oil-exchange rate portfolios after noise is removed from the original data.

Fast Collisional Lipid Transfer Among Polymer-Bounded Nanodiscs

NASA Astrophysics Data System (ADS)

Cuevas Arenas, Rodrigo; Danielczak, Bartholomäus; Martel, Anne; Porcar, Lionel; Breyton, Cécile; Ebel, Christine; Keller, Sandro

2017-04-01

Some styrene/maleic acid (SMA) copolymers solubilise membrane lipids and proteins to form polymer-bounded nanodiscs termed SMA/lipid particles (SMALPs). Although SMALPs preserve a lipid-bilayer core, they appear to be more dynamic than other membrane mimics. We used time-resolved Förster resonance energy transfer and small-angle neutron scattering to determine the kinetics and the mechanisms of phospholipid transfer among SMALPs. In contrast with vesicles or protein-bounded nanodiscs, SMALPs exchange lipids not only by monomer diffusion but also by fast collisional transfer. Under typical experimental conditions, lipid exchange occurs within seconds in the case of SMALPs but takes minutes to days in the other bilayer particles. The diffusional and second-order collisional exchange rate constants for SMALPs at 30 °C are kdif = 0.287 s-1 and kcol = 222 M-1s-1, respectively. Together with the fast kinetics, the observed invariability of the rate constants with probe hydrophobicity and the moderate activation enthalpy of ~70 kJ mol-1 imply that lipids exchange through a “hydrocarbon continuum” enabled by the flexible nature of the SMA belt surrounding the lipid-bilayer core. Owing to their fast lipid-exchange kinetics, SMALPs represent highly dynamic equilibrium rather than kinetically trapped membrane mimics, which has important implications for studying protein/lipid interactions in polymer-bounded nanodiscs.

Characteristics of energy exchange between inter- and intramolecular degrees of freedom in crystalline 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) with implications for coarse-grained simulations of shock waves in polyatomic molecular crystals

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

Kroonblawd, Matthew P.; Sewell, Thomas D., E-mail: sewellt@missouri.edu; Maillet, Jean-Bernard, E-mail: jean-bernard.maillet@cea.fr

2016-02-14

In this report, we characterize the kinetics and dynamics of energy exchange between intramolecular and intermolecular degrees of freedom (DoF) in crystalline 1,3,5-triamino-2,4,6-trinitrobenzene (TATB). All-atom molecular dynamics (MD) simulations are used to obtain predictions for relaxation from certain limiting initial distributions of energy between the intra- and intermolecular DoF. The results are used to parameterize a coarse-grained Dissipative Particle Dynamics at constant Energy (DPDE) model for TATB. Each TATB molecule in the DPDE model is represented as an all-atom, rigid-molecule mesoparticle, with explicit external (molecular translational and rotational) DoF and coarse-grained implicit internal (vibrational) DoF. In addition to conserving linearmore » and angular momentum, the DPDE equations of motion conserve the total system energy provided that particles can exchange energy between their external and internal DoF. The internal temperature of a TATB molecule is calculated using an internal equation of state, which we develop here, and the temperatures of the external and internal DoF are coupled using a fluctuation-dissipation relation. The DPDE force expression requires specification of the input parameter σ that determines the rate at which energy is exchanged between external and internal DoF. We adjusted σ based on the predictions for relaxation processes obtained from MD simulations. The parameterized DPDE model was employed in large-scale simulations of shock compression of TATB. We show that the rate of energy exchange governed by σ can significantly influence the transient behavior of the system behind the shock.« less

Variability in Benthic Exchange Rate, Depth, and Residence Time Beneath a Shallow Coastal Estuary

NASA Astrophysics Data System (ADS)

Russoniello, Christopher J.; Heiss, James W.; Michael, Holly A.

2018-03-01

Hydrodynamically driven benthic exchange of water between the water column and shallow seabed aquifer is a significant and dynamic component of coastal and estuarine fluid budgets. Associated exchange of solutes promotes ecologically important chemical reactions, so quantifying benthic exchange rates, depths, and residence times constrains coastal chemical cycling estimates. We present the first combined field, numerical, and analytical modeling investigation of wave-induced exchange. Temporal variability of exchange was calculated with data collected by instruments deployed in a shallow estuary for 11 days. Differential pressure sensors recorded pressure gradients across the seabed, and up- and down-looking ADCPs recorded currents and pressures to determine wave parameters, surface-water currents, and water depth. Wave-induced exchange was calculated (1) directly from differential pressure measurements, and indirectly with an analytical model based on wave parameters from (2) ADCP and (3) wind data. Wave-induced exchange from pressure measurements and ADCP-measured wave parameters matched well, but both exceeded wind-based values. Exchange induced by tidal pumping and current-bed form interaction—the other primary drivers in shallow coastal waters were calculated from tidal stage variation and ADCP-measured currents. Exchange from waves (mean = 20.0 cm/d; range = 1.75-92.3 cm/d) greatly exceeded exchange due to tides (mean = 3.7 cm/d) and current-bed form interaction (mean = 6.5 × 10-2 cm/d). Groundwater flow models showed aquifer properties affect wave-driven benthic exchange: residence time and depth increased and exchange rates decreased with increasing hydraulic diffusivity (ratio of aquifer permeability to compressibility). This new understanding of benthic exchange will help managers assess its control over chemical fluxes to marine systems.

Backbone dynamics of a model membrane protein: measurement of individual amide hydrogen-exchange rates in detergent-solubilized M13 coat protein using /sup 13/C NMR hydrogen/deuterium isotope shifts

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

Henry, G.D.; Weiner, J.H.; Sykes, B.D.

Hydrogen-exchange rates have been measured for individual assigned amide protons in M13 coat protein, a 50-residue integral membrane protein, using a /sup 13/C nuclear magnetic resonance (NMR) equilibrium isotope shift technique. The locations of the more rapidly exchanging amides have been determined. In D/sub 2/O solutions, a peptide carbonyl resonance undergoes a small upfield isotope shift (0.08-0.09 ppm) from its position in H/sub 2/O solutions; in 1:1 H/sub 2/O/D/sub 2/O mixtures, the carbonyl line shape is determined by the exchange rate at the adjacent nitrogen atom. M13 coat protein was labeled biosynthetically with /sup 13/C at the peptide carbonyls ofmore » alanine, glycine, phenylalanine, proline, and lysine, and the exchange rates of 12 assigned amide protons in the hydrophilic regions were measured as a function of pH by using the isotope shift method. This equilibrium technique is sensitive to the more rapidly exchanging protons which are difficult to measure by classical exchange-out experiments. In proteins, structural factors, notably H bonding, can decrease the exchange rate of an amide proton by many orders of magnitude from that observed in the freely exposed amides of model peptides such as poly(DL-alanine). With corrections for sequence-related inductive effects, the retardation of amide exchange in sodium dodecyl sulfate solubilized coat protein has been calculated with respect to poly(DL-alanine). The most rapidly exchanging protons, which are retarded very little or not at all, are shown to occur at the N- and C-termini of the molecule. A model of the detergent-solubilized coat protein is constructed from these H-exchange data which is consistent with circular dichroism and other NMR results.« less

Experimental study of heat transfer enhancement due to the surface vibrations in a flexible double pipe heat exchanger

NASA Astrophysics Data System (ADS)

Hosseinian, A.; Meghdadi Isfahani, A. H.

2018-04-01

In this study, the heat transfer enhancement due to the surface vibration for a double pipe heat exchanger, made of PVDF, is investigated. In order to create forced vibrations (3-9 m/s2, 100 Hz) on the outer surface of the heat exchanger electro-dynamic vibrators are used. Experiments were performed at inner Reynolds numbers ranging from 2533 to 9960. The effects of volume flow rate and temperature on heat transfer performance are evaluated. Results demonstrated that heat transfer coefficient increases by increasing vibration level and mass flow rate. The most increase in heat transfer coefficient is 97% which is obtained for the highest vibration level (9 m/s2) in the experiment range.

Variability in benthic exchange rate, depth, and residence time beneath a shallow coastal estuary

NASA Astrophysics Data System (ADS)

Russoniello, C. J.; Michael, H. A.; Heiss, J.

2017-12-01

Hydrodynamically-driven exchange of water between the water column and shallow seabed aquifer, benthic exchange, is a significant and dynamic component of coastal and estuarine fluid budgets, but wave-induced benthic exchange has not been measured in the field. Mixing between surface water and groundwater solutes promotes ecologically important chemical reactions, so quantifying benthic exchange rates, depths, and residence times, constrains estimates of coastal chemical cycling. In this study, we present the first field-based direct measurements of wave-induced exchange and compare it to exchange induced by the other primary drivers of exchange - tides, and currents. We deployed instruments in a shallow estuary to measure benthic exchange and temporal variability over an 11-day period. Differential pressure sensors recorded pressure gradients across the seabed, and up-and down-looking ADCPs recorded currents and pressures from which wave parameters, surface-water currents, and water depth were determined. Wave-induced exchange was calculated directly from 1) differential pressure measurements, and indirectly with an analytical solution based on wave parameters from 2) ADCP and 3) weather station data. Groundwater flow models were used to assess the effects of aquifer properties on benthic exchange depth and residence time. Benthic exchange driven by tidal pumping or current-bedform interaction was calculated from tidal stage variation and from ADCP-measured currents at the bed, respectively. Waves were the primary benthic exchange driver (average = 20.0 cm/d, maximum = 92.3 cm/d) during the measurement period. Benthic exchange due to tides (average = 3.7 cm/d) and current-bedform interaction (average = 6.5x10-2 cm/d) was much lower. Wave-induced exchange calculated from pressure measurements and ADCP-measured wave parameters matched well, but wind-based rates underestimated wave energy and exchange. Groundwater models showed that residence time and depth increased in high-permeability, incompressible aquifers, and exchange rates increased in low-permeability, compressible aquifers. These findings support and extend the utility of existing wave-induced exchange solutions and will help managers assess the importance of benthic exchange on coastal chemical cycling.

The use of fibrous ion exchangers in gold hydrometallurgy

NASA Astrophysics Data System (ADS)

Kautzmann, R. M.; Sampaio, C. H.; Cortina, J. L.; Soldatov, V.; Shunkevich, A.

2002-10-01

This article examines a family of ion-exchange fibers, FIBAN, containing primary and secondary amine groups. These ion exchangers have a fiber diameter of 20 40 Μm, high osmotic and mechanic stability, a high rate of adsorption and regeneration, and excellent dynamic characteristics as filtering media. Inparticular, this article discusses the use of FIBAN fibrous ion exchangers in the recovery of gold cyanide andbase-metal cyanides (copper and mercury) from mineral-leaching solutions. The influence of polymer structure and water content on their extraction ability is described, along with key parameters of gold hydrometallurgy such as extraction efficiency, selectivity, pH dependence, gold cyanide loading, kinetics, and stripping.

El Niño Southern Oscillation (ENSO) Enhances CO2 Exchange Rates in Freshwater Marsh Ecosystems in the Florida Everglades

PubMed Central

Malone, Sparkle L.; Staudhammer, Christina L.; Oberbauer, Steven F.; Olivas, Paulo; Ryan, Michael G.; Schedlbauer, Jessica L.; Loescher, Henry W.; Starr, Gregory

2014-01-01

This research examines the relationships between El Niño Southern Oscillation (ENSO), water level, precipitation patterns and carbon dioxide (CO2) exchange rates in the freshwater wetland ecosystems of the Florida Everglades. Data was obtained over a 5-year study period (2009–2013) from two freshwater marsh sites located in Everglades National Park that differ in hydrology. At the short-hydroperiod site (Taylor Slough; TS) and the long-hydroperiod site (Shark River Slough; SRS) fluctuations in precipitation patterns occurred with changes in ENSO phase, suggesting that extreme ENSO phases alter Everglades hydrology which is known to have a substantial influence on ecosystem carbon dynamics. Variations in both ENSO phase and annual net CO2 exchange rates co-occurred with changes in wet and dry season length and intensity. Combined with site-specific seasonality in CO2 exchanges rates, El Niño and La Niña phases magnified season intensity and CO2 exchange rates at both sites. At TS, net CO2 uptake rates were higher in the dry season, whereas SRS had greater rates of carbon sequestration during the wet season. As La Niña phases were concurrent with drought years and extended dry seasons, TS became a greater sink for CO2 on an annual basis (−11 to −110 g CO2 m−2 yr−1) compared to El Niño and neutral years (−5 to −43.5 g CO2 m−2 yr−1). SRS was a small source for CO2 annually (1.81 to 80 g CO2 m−2 yr−1) except in one exceptionally wet year that was associated with an El Niño phase (−16 g CO2 m−2 yr−1). Considering that future climate predictions suggest a higher frequency and intensity in El Niño and La Niña phases, these results indicate that changes in extreme ENSO phases will significantly alter CO2 dynamics in the Florida Everglades. PMID:25521299

Scaling Exponents in Financial Markets

NASA Astrophysics Data System (ADS)

Kim, Kyungsik; Kim, Cheol-Hyun; Kim, Soo Yong

2007-03-01

We study the dynamical behavior of four exchange rates in foreign exchange markets. A detrended fluctuation analysis (DFA) is applied to detect the long-range correlation embedded in the non-stationary time series. It is for our case found that there exists a persistent long-range correlation in volatilities, which implies the deviation from the efficient market hypothesis. Particularly, the crossover is shown to exist in the scaling behaviors of the volatilities.

The dynamics of multimer formation of the amphiphilic hydrophobin protein HFBII.

PubMed

Grunér, M S; Paananen, A; Szilvay, G R; Linder, M B

2017-07-01

Hydrophobins are surface-active proteins produced by filamentous fungi. They have amphiphilic structures and form multimers in aqueous solution to shield their hydrophobic regions. The proteins rearrange at interfaces and self-assemble into films that can show a very high degree of structural order. Little is known on dynamics of multimer interactions in solution and how this is affected by other components. In this work we examine the multimer dynamics by stopped-flow fluorescence measurements and Förster Resonance Energy Transfer (FRET) using the class II hydrophobin HFBII. The half-life of exchange in the multimer state was 0.9s at 22°C with an activation energy of 92kJ/mol. The multimer exchange process of HFBII was shown to be significantly affected by the closely related HFBI hydrophobin, lowering both activation energy and half-life for exchange. Lower molecular weight surfactants interacted in very selective ways, but other surface active proteins did not influence the rates of exchange. The results indicate that the multimer formation is driven by specific molecular interactions that distinguish different hydrophobins from each other. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Understanding Unimer Exchange Processes in Block Copolymer Micelles using NMR Diffusometry, Time-Resolved NMR, and SANS

NASA Astrophysics Data System (ADS)

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

Our team seeks to understand dynamic behaviors of block copolymer micelles and their interplay with encapsulated cargo molecules. Quantifying unimer and cargo exchange rates micelles can provide critical information for determining mechanisms of unimer exchange as well as designing systems for specific cargo release dynamics. We are exploring the utility of NMR spectroscopy and diffusometry techniques as complements to existing SANS and fluorescence methods. One promising new method involves time-resolved NMR spin relaxation measurements, wherein mixing of fully protonated and 2H-labeled PEO-b-PCL micelles solutions shows an increase in spin-lattice relaxation time (T1) with time after mixing. This is due to a weakening in magnetic environment surrounding 1H spins as 2H-bearing unimers join fully protonated micelles. We are measuring time constants for unimer exchange of minutes to hours, and we expect to resolve times of <1 min. This method can work on any solution NMR spectrometer and with minimal perturbation to chemical structure (as in dye-labelled fluorescence methods). Multimodal NMR can complement existing characterization tools, expanding and accelerating dynamics measurements for polymer micelle, nanogel, and nanoparticle developers.

Barrierless association of CF2 and dissociation of C2F4 by variational transition-state theory and system-specific quantum Rice–Ramsperger–Kassel theory

PubMed Central

Bao, Junwei Lucas; Zhang, Xin

2016-01-01

Bond dissociation is a fundamental chemical reaction, and the first principles modeling of the kinetics of dissociation reactions with a monotonically increasing potential energy along the dissociation coordinate presents a challenge not only for modern electronic structure methods but also for kinetics theory. In this work, we use multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) to compute the high-pressure limit dissociation rate constant of tetrafluoroethylene (C2F4), in which the potential energies are computed by direct dynamics with the M08-HX exchange correlation functional. To treat the pressure dependence of the unimolecular rate constants, we use the recently developed system-specific quantum Rice–Ramsperger–Kassel theory. The calculations are carried out by direct dynamics using an exchange correlation functional validated against calculations that go beyond coupled-cluster theory with single, double, and triple excitations. Our computed dissociation rate constants agree well with the recent experimental measurements. PMID:27834727

Barrierless association of CF2 and dissociation of C2F4 by variational transition-state theory and system-specific quantum Rice-Ramsperger-Kassel theory.

PubMed

Bao, Junwei Lucas; Zhang, Xin; Truhlar, Donald G

2016-11-29

Bond dissociation is a fundamental chemical reaction, and the first principles modeling of the kinetics of dissociation reactions with a monotonically increasing potential energy along the dissociation coordinate presents a challenge not only for modern electronic structure methods but also for kinetics theory. In this work, we use multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) to compute the high-pressure limit dissociation rate constant of tetrafluoroethylene (C 2 F 4 ), in which the potential energies are computed by direct dynamics with the M08-HX exchange correlation functional. To treat the pressure dependence of the unimolecular rate constants, we use the recently developed system-specific quantum Rice-Ramsperger-Kassel theory. The calculations are carried out by direct dynamics using an exchange correlation functional validated against calculations that go beyond coupled-cluster theory with single, double, and triple excitations. Our computed dissociation rate constants agree well with the recent experimental measurements.

Connectionist Architectures for Time Series Prediction of Dynamical Systems

NASA Astrophysics Data System (ADS)

Weigend, Andreas Sebastian

We investigate the effectiveness of connectionist networks for predicting the future continuation of temporal sequences. The problem of overfitting, particularly serious for short records of noisy data, is addressed by the method of weight-elimination: a term penalizing network complexity is added to the usual cost function in back-propagation. We describe the dynamics of the procedure and clarify the meaning of the parameters involved. From a Bayesian perspective, the complexity term can be usefully interpreted as an assumption about prior distribution of the weights. We analyze three time series. On the benchmark sunspot series, the networks outperform traditional statistical approaches. We show that the network performance does not deteriorate when there are more input units than needed. In the second example, the notoriously noisy foreign exchange rates series, we pick one weekday and one currency (DM vs. US). Given exchange rate information up to and including a Monday, the task is to predict the rate for the following Tuesday. Weight-elimination manages to extract a significant part of the dynamics and makes the solution interpretable. In the third example, the networks predict the resource utilization of a chaotic computational ecosystem for hundreds of steps forward in time.

Ion Exchange Technology Development in Support of the Urine Processor Assembly Precipitation Prevention Project for the International Space Station

NASA Technical Reports Server (NTRS)

Mitchell, Julie L.; Broyan, James L.; Pickering, Karen D.; Adam, Niklas; Casteel, Michael; Callaham, Michael; Carrier, Chris

2011-01-01

In support of the Urine Processor Assembly Precipitation Prevention Project (UPA PPP), multiple technologies were explored to prevent CaSO4 dot 2H2O (gypsum) precipitation during the on-orbit distillation process. Gypsum precipitation currently limits the water recovery rate onboard the International Space Station (ISS) to 70% versus the planned 85% target water recovery rate. Due to its advanced performance in removing calcium cations in pretreated augmented urine (PTAU), ion exchange was selected as one of the technologies for further development by the PPP team. A total of 12 ion exchange resins were evaluated in various equilibrium and dynamic column tests with solutions of dissolved gypsum, urine ersatz, PTAU, and PTAU brine at 85% water recovery. While initial evaluations indicated that the Purolite SST60 resin had the highest calcium capacity in PTAU (0.30 meq/mL average), later tests showed that the Dowex G26 and Amberlite FPC12H resins had the highest capacity (0.5 meq/mL average). Further dynamic column testing proved that G26 performance is +/- 10% of that value at flow rates of 0.45 and 0.79 Lph under continuous flow, and 10.45 Lph under pulsed flow. Testing at the Marshall Spaceflight Center (MSFC) integrates the ion exchange technology with a UPA ground article under flight-like pulsed flow conditions with PTAU. To date, no gypsum precipitation has taken place in any of the initial evaluations.

Seasonal soil VOC exchange rates in a Mediterranean holm oak forest and their responses to drought conditions

NASA Astrophysics Data System (ADS)

Asensio, Dolores; Peñuelas, Josep; Ogaya, Romà; Llusià, Joan

Available information on soil volatile organic compound (VOC) exchange, emissions and uptake, is very scarce. We here describe the amounts and seasonality of soil VOC exchange during a year in a natural Mediterranean holm oak forest growing in Southern Catalonia. We investigated changes in soil VOC dynamics in drought conditions by decreasing the soil moisture to 30% of ambient conditions by artificially excluding rainfall and water runoff, and predicted the response of VOC exchange to the drought forecasted in the Mediterranean region for the next decades by GCM and ecophysiological models. The annual average of the total (detected) soil VOC and total monoterpene exchange rates were 3.2±3.2 and -0.4±0.3 μg m -2 h -1, respectively, in control plots. These values represent 0.003% of the total C emitted by soil at the study site as CO 2 whereas the annual mean of soil monoterpene exchange represents 0.0004% of total C. Total soil VOC exchange rates in control plots showed seasonal variations following changes in soil moisture and phenology. Maximum values were found in spring (17±8 μg m -2 h -1). Although there was no significant global effect of drought treatment on the total soil VOC exchange rates, annual average of total VOC exchange rates in drought plots resulted in an uptake rate (-0.5±1.8 μg m -2 h -1) instead of positive net emission rates. Larger soil VOC and monoterpene exchanges were measured in drought plots than in control plots in summer, which might be mostly attributable to autotrophic (roots) metabolism. The results show that the diversity and magnitude of monoterpene and VOC soil emissions are low compared with plant emissions, that they are driven by soil moisture, that they represent a very small part of the soil-released carbon and that they may be strongly reduced or even reversed into net uptakes by the predicted decreases of soil water availability in the next decades. In all cases, it seems that VOC fluxes in soil might have greater impact on soil ecology than on atmospheric chemistry.

Asynchronous Replica Exchange Software for Grid and Heterogeneous Computing.

PubMed

Gallicchio, Emilio; Xia, Junchao; Flynn, William F; Zhang, Baofeng; Samlalsingh, Sade; Mentes, Ahmet; Levy, Ronald M

2015-11-01

Parallel replica exchange sampling is an extended ensemble technique often used to accelerate the exploration of the conformational ensemble of atomistic molecular simulations of chemical systems. Inter-process communication and coordination requirements have historically discouraged the deployment of replica exchange on distributed and heterogeneous resources. Here we describe the architecture of a software (named ASyncRE) for performing asynchronous replica exchange molecular simulations on volunteered computing grids and heterogeneous high performance clusters. The asynchronous replica exchange algorithm on which the software is based avoids centralized synchronization steps and the need for direct communication between remote processes. It allows molecular dynamics threads to progress at different rates and enables parameter exchanges among arbitrary sets of replicas independently from other replicas. ASyncRE is written in Python following a modular design conducive to extensions to various replica exchange schemes and molecular dynamics engines. Applications of the software for the modeling of association equilibria of supramolecular and macromolecular complexes on BOINC campus computational grids and on the CPU/MIC heterogeneous hardware of the XSEDE Stampede supercomputer are illustrated. They show the ability of ASyncRE to utilize large grids of desktop computers running the Windows, MacOS, and/or Linux operating systems as well as collections of high performance heterogeneous hardware devices.

Molecular Dynamics Simulations Provide Atomistic Insight into Hydrogen Exchange Mass Spectrometry Experiments.

PubMed

Petruk, Ariel A; Defelipe, Lucas A; Rodríguez Limardo, Ramiro G; Bucci, Hernán; Marti, Marcelo A; Turjanski, Adrian G

2013-01-08

It is now clear that proteins are flexible entities that in solution switch between conformations to achieve their function. Hydrogen/Deuterium Exchange Mass Spectrometry (HX/MS) is an invaluable tool to understand dynamic changes in proteins modulated by cofactor binding, post-transductional modifications, or protein-protein interactions. ERK2MAPK, a protein involved in highly conserved signal transduction pathways of paramount importance for normal cellular function, has been extensively studied by HX/MS. Experiments of the ERK2MAPK in the inactive and active states (in the presence or absence of bound ATP) have provided valuable information on the plasticity of the MAPK domain. However, interpretation of the HX/MS data is difficult, and changes are mostly explained in relation to available X-ray structures, precluding a complete atomic picture of protein dynamics. In the present work, we have used all atom Molecular Dynamics simulations (MD) to provide a theoretical framework for the interpretation of HX/MS data. Our results show that detailed analysis of protein-solvent interaction along the MD simulations allows (i) prediction of the number of protons exchanged for each peptide in the HX/MS experiments, (ii) rationalization of the experimentally observed changes in exchange rates in different protein conditions at the residue level, and (iii) that at least for ERK2MAPK, most of the functionally observed differences in protein dynamics are related to what can be considered the native state conformational ensemble. In summary, the combination of HX/MS experiments with all atom MD simulations emerges as a powerful approach to study protein native state dynamics with atomic resolution.

Lanthanide paramagnetic probes for NMR spectroscopic studies of fast molecular conformational dynamics and temperature control. Effective six-site proton exchange in 18-crown-6 by exchange spectroscopy.

PubMed

Babailov, Sergey P

2012-02-06

(1)H and (13)C NMR measurements are reported for the CDCl(3) and CD(2)Cl(2) solutions of [La(18-crown-6)(NO(3))(3)] (I), [Pr(18-crown-6) (NO(3))(3)] (II), [Ce(18-crown-6)(NO(3))(3)] (III), and [Nd(18-crown-6)(NO(3))(3)] (IV) complexes. Temperature dependencies of the (1)H NMR spectra of paramagnetic II-IV have been analyzed using the dynamic NMR (DNMR) methods for six-site exchange. Two types of conformational dynamic processes were identified (the first one is conditioned by interconversion of complex enantiomeric forms and pseudorotation of a macrocycle molecule upon the C(2) symmetry axis; the second one is conditioned by macrocycle molecule inversion). Application of exchange spectroscopy (2D-EXSY) of DNMR for investigation of this dynamic system (II-IV) simplifies the assignment of the NMR signals and represents the first experimental study of multisite exchange. In the present work, the methodology of paramagnetic 4f (Ce, Pr, and Nd) probe applications for the study of free-energy, enthalpy, and entropy changes in chemical exchange processes, as well as the advantages of this method in a comparison with DNMR studies of diamagnetic substances, is discussed. In particular, as a result of paramagnetic chemical shifts in 4f complexes, the range of measurable rate constants expands considerably compared to the analogous range in diamagnetic compounds. Coordination compounds investigated in the paper represent new types of thermometric NMR sensors and lanthanide paramagnetic probes for in situ temperature control in solution.

Inorganic carbon and oxygen dynamics in a marsh‐dominated estuary

PubMed Central

Di Iorio, Daniela; Cai, Wei‐Jun; Hopkinson, Charles S.

2017-01-01

Abstract We conducted a free‐water mass balance‐based study to address the rate of metabolism and net carbon exchange for the tidal wetland and estuarine portion of the coastal ocean and the uncertainties associated with this approach were assessed. We measured open water diurnal O2 and dissolved inorganic carbon (DIC) dynamics seasonally in a salt marsh‐estuary in Georgia, U.S.A. with a focus on the marsh‐estuary linkage associated with tidal flooding. We observed that the overall estuarine system was a net source of CO2 to the atmosphere and coastal ocean and a net sink for oceanic and atmospheric O2. Rates of metabolism were extremely high, with respiration (43 mol m−2 yr−1) greatly exceeding gross primary production (28 mol m−2 yr−1), such that the overall system was net heterotrophic. Metabolism measured with DIC were higher than with O2, which we attribute to high rates of anaerobic respiration and reduced sulfur storage in salt marsh sediments, and we assume substantial levels of anoxygenic photosynthesis. We found gas exchange from a flooded marsh is substantial, accounting for about 28% of total O2 and CO2 air–water exchange. A significant percentage of the overall estuarine aquatic metabolism is attributable to metabolism of marsh organisms during inundation. Our study suggests not rely on oceanographic stoichiometry to convert from O2 to C based measurements when constructing C balances for the coastal ocean. We also suggest eddy covariance measurements of salt marsh net ecosystem exchange underestimate net ecosystem production as they do not account for lateral DIC exchange associated with marsh tidal inundation. PMID:29456267

Multiscale Kinetic Modeling Reveals an Ensemble of Cl–/H+ Exchange Pathways in ClC-ec1 Antiporter

PubMed Central

2018-01-01

Despite several years of research, the ion exchange mechanisms in chloride/proton antiporters and many other coupled transporters are not yet understood at the molecular level. Here, we present a novel approach to kinetic modeling and apply it to ion exchange in ClC-ec1. Our multiscale kinetic model is developed by (1) calculating the state-to-state rate coefficients with reactive and polarizable molecular dynamics simulations, (2) optimizing these rates in a global kinetic network, and (3) predicting new electrophysiological results. The model shows that the robust Cl:H exchange ratio (2.2:1) can indeed arise from kinetic coupling without large protein conformational changes, indicating a possible facile evolutionary connection to chloride channels. The E148 amino acid residue is shown to couple chloride and proton transport through protonation-dependent blockage of the central anion binding site and an anion-dependent pKa value, which influences proton transport. The results demonstrate how an ensemble of different exchange pathways, as opposed to a single series of transitions, culminates in the macroscopic observables of the antiporter, such as transport rates, chloride/proton stoichiometry, and pH dependence. PMID:29332400

Riverbed Hydrologic Exchange Dynamics in a Large Regulated River Reach

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

Zhou, Tian; Bao, Jie; Huang, Maoyi

Hydrologic exchange flux (HEF) is an important hydrologic component in river corridors that includes both bidirectional (hyporheic) and unidirectional (gaining/losing) surface water – groundwater exchanges. Quantifying HEF rates in a large regulated river is difficult due to the large spatial domains, complexity of geomorphologic features and subsurface properties, and the great stage variations created by dam operations at multiple time scales. In this study, we developed a method that combined numerical modeling and field measurements for estimating HEF rates across the river bed in a 7‐km long reach of the highly regulated Columbia River. A high‐resolution computational fluid dynamics (CFD)more » modeling framework was developed and validated by field measurements and other modeling results to characterize the HEF dynamics across the river bed. We found that about 85% of the time from 2008‐2014 the river was losing water with an annual average net HEF rates across the river bed (Qz) of ‐2.3 m3 s−1 (negative indicating downwelling). June was the only month that the river gained water, with monthly averaged Qz of 0.8 m3 s−1. We also found that the daily dam operations increased the hourly gross gaining and losing rate over an average year of 8% and 2%, respectively. By investigating the HEF feedbacks at various time scales, we suggest that the dam operations could reduce the HEF at seasonal time scale by decreasing the seasonal flow variations, while also enhance the HEF at sub‐daily time scale by generating high frequency discharge variations. These changes could generate significant impacts on biogeochemical processes in the hyporheic zone.« less

Stochastic GARCH dynamics describing correlations between stocks

NASA Astrophysics Data System (ADS)

Prat-Ortega, G.; Savel'ev, S. E.

2014-09-01

The ARCH and GARCH processes have been successfully used for modelling price dynamics such as stock returns or foreign exchange rates. Analysing the long range correlations between stocks, we propose a model, based on the GARCH process, which is able to describe the main characteristics of the stock price correlations, including the mean, variance, probability density distribution and the noise spectrum.

Continental faunal exchange and the asymmetrical radiation of carnivores.

PubMed

Pires, Mathias M; Silvestro, Daniele; Quental, Tiago B

2015-10-22

Lineages arriving on islands may undergo explosive evolutionary radiations owing to the wealth of ecological opportunities. Although studies on insular taxa have improved our understanding of macroevolutionary phenomena, we know little about the macroevolutionary dynamics of continental exchanges. Here we study the evolution of eight Carnivora families that have migrated across the Northern Hemisphere to investigate if continental invasions also result in explosive diversification dynamics. We used a Bayesian approach to estimate speciation and extinction rates from a substantial dataset of fossil occurrences while accounting for the incompleteness of the fossil record. Our analyses revealed a strongly asymmetrical pattern in which North American lineages invading Eurasia underwent explosive radiations, whereas lineages invading North America maintained uniform diversification dynamics. These invasions into Eurasia were characterized by high rates of speciation and extinction. The radiation of the arriving lineages in Eurasia coincide with the decline of established lineages or phases of climate change, suggesting differences in the ecological settings between the continents may be responsible for the disparity in diversification dynamics. These results reveal long-term outcomes of biological invasions and show that the importance of explosive radiations in shaping diversity extends beyond insular systems and have significant impact at continental scales. © 2015 The Author(s).

Continental faunal exchange and the asymmetrical radiation of carnivores

PubMed Central

Pires, Mathias M.; Silvestro, Daniele; Quental, Tiago B.

2015-01-01

Lineages arriving on islands may undergo explosive evolutionary radiations owing to the wealth of ecological opportunities. Although studies on insular taxa have improved our understanding of macroevolutionary phenomena, we know little about the macroevolutionary dynamics of continental exchanges. Here we study the evolution of eight Carnivora families that have migrated across the Northern Hemisphere to investigate if continental invasions also result in explosive diversification dynamics. We used a Bayesian approach to estimate speciation and extinction rates from a substantial dataset of fossil occurrences while accounting for the incompleteness of the fossil record. Our analyses revealed a strongly asymmetrical pattern in which North American lineages invading Eurasia underwent explosive radiations, whereas lineages invading North America maintained uniform diversification dynamics. These invasions into Eurasia were characterized by high rates of speciation and extinction. The radiation of the arriving lineages in Eurasia coincide with the decline of established lineages or phases of climate change, suggesting differences in the ecological settings between the continents may be responsible for the disparity in diversification dynamics. These results reveal long-term outcomes of biological invasions and show that the importance of explosive radiations in shaping diversity extends beyond insular systems and have significant impact at continental scales. PMID:26490792

Lutetium(iii) aqua ion: On the dynamical structure of the heaviest lanthanoid hydration complex

NASA Astrophysics Data System (ADS)

Sessa, Francesco; Spezia, Riccardo; D'Angelo, Paola

2016-05-01

The structure and dynamics of the lutetium(iii) ion in aqueous solution have been investigated by means of a polarizable force field molecular dynamics (MD). An 8-fold square antiprism (SAP) geometry has been found to be the dominant configuration of the lutetium(iii) aqua ion. Nevertheless, a low percentage of 9-fold complexes arranged in a tricapped trigonal prism (TTP) geometry has been also detected. Dynamic properties have been explored by carrying out six independent MD simulations for each of four different temperatures: 277 K, 298 K, 423 K, 632 K. The mean residence time of water molecules in the first hydration shell at room temperature has been found to increase as compared to the central elements of the lanthanoid series in agreement with previous experimental findings. Water exchange kinetic rate constants at each temperature and activation parameters of the process have been determined from the MD simulations. The obtained structural and dynamical results suggest that the water exchange process for the lutetium(iii) aqua ion proceeds with an associative mechanism, in which the SAP hydration complex undergoes temporary structural changes passing through a 9-fold TTP intermediate. Such results are consistent with the water exchange mechanism proposed for heavy lanthanoid atoms.

Lutetium(III) aqua ion: On the dynamical structure of the heaviest lanthanoid hydration complex

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

Sessa, Francesco; D’Angelo, Paola, E-mail: p.dangelo@uniroma1.it; Spezia, Riccardo

2016-05-28

The structure and dynamics of the lutetium(III) ion in aqueous solution have been investigated by means of a polarizable force field molecular dynamics (MD). An 8-fold square antiprism (SAP) geometry has been found to be the dominant configuration of the lutetium(III) aqua ion. Nevertheless, a low percentage of 9-fold complexes arranged in a tricapped trigonal prism (TTP) geometry has been also detected. Dynamic properties have been explored by carrying out six independent MD simulations for each of four different temperatures: 277 K, 298 K, 423 K, 632 K. The mean residence time of water molecules in the first hydration shellmore » at room temperature has been found to increase as compared to the central elements of the lanthanoid series in agreement with previous experimental findings. Water exchange kinetic rate constants at each temperature and activation parameters of the process have been determined from the MD simulations. The obtained structural and dynamical results suggest that the water exchange process for the lutetium(III) aqua ion proceeds with an associative mechanism, in which the SAP hydration complex undergoes temporary structural changes passing through a 9-fold TTP intermediate. Such results are consistent with the water exchange mechanism proposed for heavy lanthanoid atoms.« less

Lutetium(iii) aqua ion: On the dynamical structure of the heaviest lanthanoid hydration complex.

PubMed

Sessa, Francesco; Spezia, Riccardo; D'Angelo, Paola

2016-05-28

The structure and dynamics of the lutetium(iii) ion in aqueous solution have been investigated by means of a polarizable force field molecular dynamics (MD). An 8-fold square antiprism (SAP) geometry has been found to be the dominant configuration of the lutetium(iii) aqua ion. Nevertheless, a low percentage of 9-fold complexes arranged in a tricapped trigonal prism (TTP) geometry has been also detected. Dynamic properties have been explored by carrying out six independent MD simulations for each of four different temperatures: 277 K, 298 K, 423 K, 632 K. The mean residence time of water molecules in the first hydration shell at room temperature has been found to increase as compared to the central elements of the lanthanoid series in agreement with previous experimental findings. Water exchange kinetic rate constants at each temperature and activation parameters of the process have been determined from the MD simulations. The obtained structural and dynamical results suggest that the water exchange process for the lutetium(iii) aqua ion proceeds with an associative mechanism, in which the SAP hydration complex undergoes temporary structural changes passing through a 9-fold TTP intermediate. Such results are consistent with the water exchange mechanism proposed for heavy lanthanoid atoms.

Extensions to the Dynamic Aerospace Vehicle Exchange Markup Language

NASA Technical Reports Server (NTRS)

Brian, Geoffrey J.; Jackson, E. Bruce

2011-01-01

The Dynamic Aerospace Vehicle Exchange Markup Language (DAVE-ML) is a syntactical language for exchanging flight vehicle dynamic model data. It provides a framework for encoding entire flight vehicle dynamic model data packages for exchange and/or long-term archiving. Version 2.0.1 of DAVE-ML provides much of the functionality envisioned for exchanging aerospace vehicle data; however, it is limited in only supporting scalar time-independent data. Additional functionality is required to support vector and matrix data, abstracting sub-system models, detailing dynamics system models (both discrete and continuous), and defining a dynamic data format (such as time sequenced data) for validation of dynamics system models and vehicle simulation packages. Extensions to DAVE-ML have been proposed to manage data as vectors and n-dimensional matrices, and record dynamic data in a compatible form. These capabilities will improve the clarity of data being exchanged, simplify the naming of parameters, and permit static and dynamic data to be stored using a common syntax within a single file; thereby enhancing the framework provided by DAVE-ML for exchanging entire flight vehicle dynamic simulation models.

Structure and dynamics of a detergent-solubilized membrane protein: measurement of amide hydrogen exchange rates in M13 coat protein by /sub 1/H NMR spectroscopy

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

O'Neil, J.D.J.; Sykes, B.D.

The coat protein of bacteriophage M13 is inserted into the inner membrane of Escherichia coli where it exists as an integral membrane protein during the reproductive cycle of the phage. The protein sequence consists of a highly hydrophobic 19-residue central segment flanked by an acidic 20-residue N-terminus and a basic 11-residue C-terminus. The authors have measured backbone amide hydrogen exchange of the protein solubilized in perdeuteriated sodium dodecyl sulfate using /sup 1/H nuclear magnetic resonance (NMR) spectroscopy. Direct proton exchange-out measurements in D/sub 2/O at 24 /sup 0/C were used to follow the exchange of the slowest amides in themore » protein. Multiple exponential fitting of the exchange data showed that these amides exchanged in two kinetic sets with exchange rates that differed by more than 100-fold. Steady-state saturation-transfer techniques were also used to measure exchange. These methods showed that 15-20 amides in the protein are very stable at 55/sup 0/C and that bout 30 amides have exchange rates retarded by at least 10/sup 5/-fold at 24/sup 0/C. Saturation-transfer studies also showed that the pH dependence of exchange in the hydrophilic termini was unusual. Relaxation and solid-state NMR experiments have previously shown that the majority of the protein backbone is rigid on the picosecond to microsecond time scale, except for the extreme ends of the molecule which are mobile. The hydrogen exchange results, which are sensitive to a much longer time scale, suggest a stable core with a progressive increase in amplitude or frequency of motions as the ends of the protein are approached.« less

Computational fluid dynamics modeling of transport and deposition of pesticides in an aircraft cabin

PubMed Central

Isukapalli, Sastry S.; Mazumdar, Sagnik; George, Pradeep; Wei, Binnian; Jones, Byron; Weisel, Clifford P.

2015-01-01

Spraying of pesticides in aircraft cabins is required by some countries as part of a disinsection process to kill insects that pose a public health threat. However, public health concerns remain regarding exposures of cabin crew and passengers to pesticides in aircraft cabins. While large scale field measurements of pesticide residues and air concentrations in aircraft cabins scenarios are expensive and time consuming, Computational Fluid Dynamics (CFD) models provide an effective alternative for characterizing concentration distributions and exposures. This study involved CFD modeling of a twin-aisle 11 row cabin mockup with heated manikins, mimicking a part of a fully occupied Boeing 767 cabin. The model was applied to study the flow and deposition of pesticides under representative scenarios with different spraying patterns (sideways and overhead) and cabin air exchange rates (low and high). Corresponding spraying experiments were conducted in the cabin mockup, and pesticide deposition samples were collected at the manikin’s lap and seat top for a limited set of five seats. The CFD model performed well for scenarios corresponding to high air exchange rates, captured the concentration profiles for middle seats under low air exchange rates, and underestimated the concentrations at window seats under low air exchange rates. Additionally, both the CFD and experimental measurements showed no major variation in deposition characteristics between sideways and overhead spraying. The CFD model can estimate concentration fields and deposition profiles at very high resolutions, which can be used for characterizing the overall variability in air concentrations and surface loadings. Additionally, these model results can also provide a realistic range of surface and air concentrations of pesticides in the cabin that can be used to estimate potential exposures of cabin crew and passengers to these pesticides. PMID:25642134

Adherent nanoparticles-mediated micro- and nanobubble nucleation

NASA Astrophysics Data System (ADS)

Chan, Chon U.; Chen, Long Quan; Lippert, Alexander; Arora, Manish; Ohl, Claus-Dieter

2014-11-01

Surface nanobubbles are commonly nucleated through water-ethanol-water exchange. It is believed that the higher gas solubility in ethanol and exothermic mixing leads to a supersaturation of gas in water. However details of the nucleation dynamic are still unknown. Here we apply the exchange process onto a glass surface deposited with nanoparticles and monitor the dynamics optically at video frame rates. During exchange bubbles of a few micron in diameter nucleate at the sites of nanoparticles. These microbubbles eventually dissolve in ethanol but are stable in water. This agrees with the nucleation process observed for surface nanobubbles. Also we find a reduction of surface attached nanobubbles near the particles, which might be due to gas uptake from the microbubble growth. Finally, high speed recordings reveal stick-slip motion of the triple contact line during the growth process. We will discuss possibilities of utilizing the findings for contamination detection and ultrasonic cleaning.

Inference of financial networks using the normalised mutual information rate.

PubMed

Goh, Yong Kheng; Hasim, Haslifah M; Antonopoulos, Chris G

2018-01-01

In this paper, we study data from financial markets, using the normalised Mutual Information Rate. We show how to use it to infer the underlying network structure of interrelations in the foreign currency exchange rates and stock indices of 15 currency areas. We first present the mathematical method and discuss its computational aspects, and apply it to artificial data from chaotic dynamics and to correlated normal-variates data. We then apply the method to infer the structure of the financial system from the time-series of currency exchange rates and stock indices. In particular, we study and reveal the interrelations among the various foreign currency exchange rates and stock indices in two separate networks, of which we also study their structural properties. Our results show that both inferred networks are small-world networks, sharing similar properties and having differences in terms of assortativity. Importantly, our work shows that global economies tend to connect with other economies world-wide, rather than creating small groups of local economies. Finally, the consistent interrelations depicted among the 15 currency areas are further supported by a discussion from the viewpoint of economics.

Inference of financial networks using the normalised mutual information rate

PubMed Central

2018-01-01

In this paper, we study data from financial markets, using the normalised Mutual Information Rate. We show how to use it to infer the underlying network structure of interrelations in the foreign currency exchange rates and stock indices of 15 currency areas. We first present the mathematical method and discuss its computational aspects, and apply it to artificial data from chaotic dynamics and to correlated normal-variates data. We then apply the method to infer the structure of the financial system from the time-series of currency exchange rates and stock indices. In particular, we study and reveal the interrelations among the various foreign currency exchange rates and stock indices in two separate networks, of which we also study their structural properties. Our results show that both inferred networks are small-world networks, sharing similar properties and having differences in terms of assortativity. Importantly, our work shows that global economies tend to connect with other economies world-wide, rather than creating small groups of local economies. Finally, the consistent interrelations depicted among the 15 currency areas are further supported by a discussion from the viewpoint of economics. PMID:29420644

Heat and water rate transfer processes in the human respiratory tract at various altitudes.

PubMed

Kandjov, I M

2001-02-01

The process of the respiratory air conditioning as a process of heat and mass exchange at the interface inspired air-airways surface was studied. Using a model of airways (Olson et al., 1970) where the segments of the respiratory tract are like cylinders with a fixed length and diameter, the corresponding heat transfer equations, in the paper are founded basic rate exchange parameters-convective heat transfer coefficient h(c)(W m(-2) degrees C(-1)) and evaporative heat transfer coefficient h(e)(W m(-2)hPa(-1)). The rate transfer parameters assumed as sources with known heat power are connected to airflow rate in different airways segments. Relationships expressing warming rate of inspired air due to convection, warming rate of inspired air due to evaporation, water diffused in the inspired air from the airways wall, i.e. a system of air conditioning parameters, was composed. The altitude dynamics of the relations is studied. Every rate conditioning parameter is an increasing function of altitude. The process of diffusion in the peripheral bronchial generations as a basic transfer process is analysed. The following phenomenon is in effect: the diffusion coefficient increases with altitude and causes a compensation of simultaneous decreasing of O(2)and CO(2)densities in atmospheric air. Due to this compensation, the diffusion in the peripheral generations with altitude is approximately constant. The elements of the human anatomy optimality as well as the established dynamics are discussed and assumed. The square form of the airways after the trachea expressed in terms of transfer supposes (in view of maximum contact surface), that a maximum heat and water exchange is achieved, i.e. high degree of air condition at fixed environmental parameters and respiration regime. Copyright 2001 Academic Press.

Thymosin-beta(4) changes the conformation and dynamics of actin monomers.

PubMed Central

De La Cruz, E M; Ostap, E M; Brundage, R A; Reddy, K S; Sweeney, H L; Safer, D

2000-01-01

Thymosin-beta(4) (Tbeta(4)) binds actin monomers stoichiometrically and maintains the bulk of the actin monomer pool in metazoan cells. Tbeta(4) binding quenches the fluorescence of N-iodoacetyl-N'-(5-sulfo-1-naphthyl)ethylenediamine (AEDANS) conjugated to Cys(374) of actin monomers. The K(d) of the actin-Tbeta(4) complex depends on the cation and nucleotide bound to actin but is not affected by the AEDANS probe. The different stabilities are determined primarily by the rates of dissociation. At 25 degrees C, the free energy of Tbeta(4) binding MgATP-actin is primarily enthalpic in origin but entropic for CaATP-actin. Binding is coupled to the dissociation of bound water molecules, which is greater for CaATP-actin than MgATP-actin monomers. Proteolysis of MgATP-actin, but not CaATP-actin, at Gly(46) on subdomain 2 is >12 times faster when Tbeta(4) is bound. The C terminus of Tbeta(4) contacts actin near this cleavage site, at His(40). By tritium exchange, Tbeta(4) slows the exchange rate of approximately eight rapidly exchanging amide protons on actin. We conclude that Tbeta(4) changes the conformation and structural dynamics ("breathing") of actin monomers. The conformational change may reflect the unique ability of Tbeta(4) to sequester actin monomers and inhibit nucleotide exchange. PMID:10777749

Imino proton exchange rates imply an induced-fit binding mechanism for the VEGF165-targeting aptamer, Macugen

PubMed Central

Lee, Joon-Hwa; Jucker, Fiona; Pardi, Arthur

2008-01-01

The 2′-fluoro/2′-O-methyl modified RNA aptamer Macugen is a potent inhibitor of the angiogenic regulatory protein, VEGF165. Macugen binds with high affinity to the heparin-binding domain (HBD) of VEGF165. Hydrogen exchange rates of the imino protons were measured for free Macugen and Macugen bound to the HBD or full-length VEGF to better understand the mechanism for high affinity binding. The results here show that the internal loop and hairpin loop of Macugen are highly dynamic in the free state and are greatly stabilized and/or protected from solvent upon protein binding. PMID:18485899

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

PubMed

Dang, Liem X; Chang, Tsun-Mei

2016-09-07

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

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

NASA Astrophysics Data System (ADS)

Dang, Liem X.; Chang, Tsun-Mei

2016-09-01

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

Methods for measuring exchangeable protons in glycosaminoglycans.

PubMed

Beecher, Consuelo N; Larive, Cynthia K

2015-01-01

Recent NMR studies of the exchangeable protons of GAGs in aqueous solution, including those of the amide, sulfamate, and hydroxyl moieties, have demonstrated potential for the detection of intramolecular hydrogen bonds, providing insights into secondary structure preferences. GAG amide protons are observable by NMR over wide pH and temperature ranges; however, specific solution conditions are required to reduce the exchange rate of the sulfamate and hydroxyl protons and allow their detection by NMR. Building on the vast body of knowledge on detection of hydrogen bonds in peptides and proteins, a variety of methods can be used to identify hydrogen bonds in GAGs including temperature coefficient measurements, evaluation of chemical shift differences between oligo- and monosaccharides, and relative exchange rates measured through line shape analysis and EXSY spectra. Emerging strategies to allow direct detection of hydrogen bonds through heteronuclear couplings offer promise for the future. Molecular dynamic simulations are important in this effort both to predict and confirm hydrogen bond donors and acceptors.

Shock dynamics of two-lane driven lattice gases

NASA Astrophysics Data System (ADS)

Schiffmann, Christoph; Appert-Rolland, Cécile; Santen, Ludger

2010-06-01

Driven lattice gases such as those of the ASEP model are useful tools for the modelling of various stochastic transport processes carried out by self-driven particles, such as molecular motors or vehicles in road traffic. Often these processes take place in one-dimensional systems offering several tracks to the particles, and in many cases the particles are able to change track with a given rate. In this work we consider the case of strong coupling where the rate of hopping along the tracks and the exchange rates are of the same order, and show how a phenomenological approach based on a domain wall theory can be used to describe the dynamics of the system. In particular, the domain walls on the different tracks form pairs, whose dynamics dominate the behaviour of the system.

Passive flow heat exchanger simulation for power generation from solar pond using thermoelectric generators

NASA Astrophysics Data System (ADS)

Baharin, Nuraida'Aadilia; Arzami, Amir Afiq; Singh, Baljit; Remeli, Muhammad Fairuz; Tan, Lippong; Oberoi, Amandeep

2017-04-01

In this study, a thermoelectric generator heat exchanger system was designed and simulated for electricity generation from solar pond. A thermoelectric generator heat exchanger was studied by using Computational Fluid Dynamics to simulate flow and heat transfer. A thermoelectric generator heat exchanger designed for passive in-pond flow used in solar pond for electrical power generation. A simple analysis simulation was developed to obtain the amount of electricity generated at different conditions for hot temperatures of a solar pond at different flow rates. Results indicated that the system is capable of producing electricity. This study and design provides an alternative way to generate electricity from solar pond in tropical countries like Malaysia for possible renewable energy applications.

On the structure and dynamics of the hydrated sulfite ion in aqueous solution--an ab initio QMCF MD simulation and large angle X-ray scattering study.

PubMed

Eklund, Lars; Hofer, Thomas S; Pribil, Andreas B; Rode, Bernd M; Persson, Ingmar

2012-05-07

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) formalism has been applied in conjunction to experimental large angle X-ray scattering to study the structure and dynamics of the hydrated sulfite ion in aqueous solution. The results show that there is a considerable effect of the lone electron-pair on sulfur concerning structure and dynamics in comparison with the sulfate ion with higher oxidation number and symmetry of the hydration shell. The S-O bond distance in the hydrated sulfite ion has been determined to 1.53(1) Å by both methods. The hydrogen bonds between the three water molecules bound to each sulfite oxygen are only slightly stronger than those in bulk water. The sulfite ion can therefore be regarded as a weak structure maker. The water exchange rate is somewhat slower for the sulfite ion than for the sulfate ion, τ(0.5) = 3.2 and 2.6 ps, respectively. An even more striking observation in the angular radial distribution (ARD) functions is that the for sulfite ion the water exchange takes place in close vicinity of the lone electron-pair directed at its sides, while in principle no water exchange did take place of the water molecules hydrogen bound to sulfite oxygens during the simulation time. This is also confirmed when detailed pathway analysis is conducted. The simulation showed that the water molecules hydrogen bound to the sulfite oxygens can move inside the hydration shell to the area outside the lone electron-pair and there be exchanged. On the other hand, for the hydrated sulfate ion in aqueous solution one can clearly see from the ARD that the distribution of exchange events is symmetrical around the entire hydration sphere.

Intermolecular electron-transfer mechanisms via quantitative structures and ion-pair equilibria for self-exchange of anionic (dinitrobenzenide) donors.

PubMed

Rosokha, Sergiy V; Lü, Jian-Ming; Newton, Marshall D; Kochi, Jay K

2005-05-25

Definitive X-ray structures of "separated" versus "contact" ion pairs, together with their spectral (UV-NIR, ESR) characterizations, provide the quantitative basis for evaluating the complex equilibria and intrinsic (self-exchange) electron-transfer rates for the potassium salts of p-dinitrobenzene radical anion (DNB(-)). Three principal types of ion pairs, K(L)(+)DNB(-), are designated as Classes S, M, and C via the specific ligation of K(+) with different macrocyclic polyether ligands (L). For Class S, the self-exchange rate constant for the separated ion pair (SIP) is essentially the same as that of the "free" anion, and we conclude that dinitrobenzenide reactivity is unaffected when the interionic distance in the separated ion pair is r(SIP) > or =6 Angstroms. For Class M, the dynamic equilibrium between the contact ion pair (with r(CIP) = 2.7 Angstroms) and its separated ion pair is quantitatively evaluated, and the rather minor fraction of SIP is nonetheless the principal contributor to the overall electron-transfer kinetics. For Class C, the SIP rate is limited by the slow rate of CIP right arrow over left arrow SIP interconversion, and the self-exchange proceeds via the contact ion pair by default. Theoretically, the electron-transfer rate constant for the separated ion pair is well-accommodated by the Marcus/Sutin two-state formulation when the precursor in Scheme 2 is identified as the "separated" inner-sphere complex (IS(SIP)) of cofacial DNB(-)/DNB dyads. By contrast, the significantly slower rate of self-exchange via the contact ion pair requires an associative mechanism (Scheme 3) in which the electron-transfer rate is strongly governed by cationic mobility of K(L)(+) within the "contact" precursor complex (IS(CIP)) according to the kinetics in Scheme 4.

Metabolic analyzer. [for measuring metabolic rate and breathing dynamics of human beings

NASA Technical Reports Server (NTRS)

Rummel, J. A.; Perry, C. L. (Inventor)

1974-01-01

An apparatus is described for the measurement of metabolic rate and breathing dynamics in which inhaled and exhaled breath are sensed by sealed, piston-displacement type spirometers. These spirometers electrically measure the volume of inhaled and exhaled breath. A mass spectrometer analyzes simultaneously for oxygen, carbon dioxide, nitrogen and water vapor. Computation circuits are responsive to the outputs of the spirometers, mass spectrometer, temperature, pressure and timing signals and compute oxygen consumption, carbon dioxide production, minute volume and respiratory exchange ratio. A selective indicator provides for read-out of these data at predetermined cyclic intervals.

Model of fracture of metal melts and the strength of melts under dynamic conditions

NASA Astrophysics Data System (ADS)

Mayer, P. N.; Mayer, A. E.

2015-07-01

The development of a continuum model of deformation and fracture of melts is needed for the description of the behavior of metals in extreme states, in particular, under high-current electron and ultrashort laser irradiation. The model proposed includes the equations of mechanics of a two-phase continuum and the equations of the kinetics of phase transitions. The change (exchange) of the volumes of dispersed and carrier phases and of the number of dispersed particles is described, and the energy and mass exchange between the phases due to phase transitions is taken into account. Molecular dynamic (MD) calculations are carried out with the use of the LAMMPS program. The continuum model is verified by MD, computational, and experimental data. The strength of aluminum, copper, and nickel is determined at various temperatures and strain rates. It is shown that an increase in the strain rate leads to an increase in the strength of a liquid metal, while an increase in temperature leads to a decrease in its strength.

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

PubMed

Fayer, M D

2009-01-01

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

Theoretical investigation on the mechanism and dynamics of oxo exchange of neptunyl(VI) hydroxide in aqueous solution.

PubMed

Yang, Xia; Chai, Zhifang; Wang, Dongqi

2015-03-21

Four types of reaction mechanisms for the oxo ligand exchange of monomeric and dimeric neptunyl(VI) hydroxide in aqueous solution were explored computationally using density functional theory (DFT) and ab initio classical molecular dynamics. The obtained results were compared with previous studies on the oxo exchange of uranyl hydroxide, as well as with experiments. It is found that the stable T-shaped [NpO3(OH)3](3-) intermediate is a key species for oxo exchange in the proton transfer in mononuclear Path I and binuclear Path IV, similar to the case of uranyl(VI) hydroxide. Path I is thought to be the preferred oxo exchange mechanism for neptunyl(VI) hydroxide in our calculations, due to the lower activation energy (22.7 and 13.1 kcal mol(-1) for ΔG(‡) and ΔH(‡), respectively) of the overall reaction. Path II via a cis-neptunyl structure assisted by a water molecule might be a competitive channel against Path I with a mononuclear mechanism, owing to a rapid dynamical process occurring in Path II. In Path IV with the binuclear mechanism, oxo exchange is accomplished via the interaction between [NpO2(OH)4](2-) and T-shaped [NpO3(OH)3](3-) with a low activation energy for the rate-determining step, however, the overall energy required to fulfill the reaction is slightly higher than that in mononuclear Path I, suggesting a possible binuclear process in the higher energy region. The chemical bonding evolution along the reaction pathways was discussed by using topological methodologies of the electron localization function (ELF).

Experimentally assessing molecular dynamics sampling of the protein native state conformational distribution

PubMed Central

Hernández, Griselda; Anderson, Janet S.; LeMaster, David M.

2012-01-01

The acute sensitivity to conformation exhibited by amide hydrogen exchange reactivity provides a valuable test for the physical accuracy of model ensembles developed to represent the Boltzmann distribution of the protein native state. A number of molecular dynamics studies of ubiquitin have predicted a well-populated transition in the tight turn immediately preceding the primary site of proteasome-directed polyubiquitylation Lys 48. Amide exchange reactivity analysis demonstrates that this transition is 103-fold rarer than these predictions. More strikingly, for the most populated novel conformational basin predicted from a recent 1 ms MD simulation of bovine pancreatic trypsin inhibitor (at 13% of total), experimental hydrogen exchange data indicates a population below 10−6. The most sophisticated efforts to directly incorporate experimental constraints into the derivation of model protein ensembles have been applied to ubiquitin, as illustrated by three recently deposited studies (PDB codes 2NR2, 2K39 and 2KOX). Utilizing the extensive set of experimental NOE constraints, each of these three ensembles yields a modestly more accurate prediction of the exchange rates for the highly exposed amides than does a standard unconstrained molecular simulation. However, for the less frequently exposed amide hydrogens, the 2NR2 ensemble offers no improvement in rate predictions as compared to the unconstrained MD ensemble. The other two NMR-constrained ensembles performed markedly worse, either underestimating (2KOX) or overestimating (2K39) the extent of conformational diversity. PMID:22425325

NMR Chemical Exchange as a Probe for Ligand-Binding Kinetics in a Theophylline-Binding RNA Aptamer

PubMed Central

Latham, Michael P.; Zimmermann, Grant R.; Pardi, Arthur

2009-01-01

The apparent on- and off-rate constants for theophylline binding to its RNA aptamer in the absence of Mg2+ were determined here by 2D 1H-1H NMR ZZ-exchange spectroscopy. Analysis of the build-up rate of the exchange cross peaks for several base-paired imino protons in the RNA yielded an apparent kon of 600 M-1 s-1. This small apparent kon results from the free RNA existing as a dynamic equilibrium of inactive states rapidly interconverting with a low population of active species. The data here indicate that the RNA aptamer employs a conformational selection mechanism for binding theophylline in the absence of Mg2+. The kinetic data here also explain a very unusual property of this RNA-theophylline system, slow exchange on the NMR chemical shift timescale for a weak-binding complex. To our knowledge, it is unprecedented to have such a weak binding complex (Kd ≈ 3.0 mM at 15 °C) show slow exchange on the NMR chemical shift timescale, but the results clearly demonstrate that slow exchange and weak binding are readily rationalized by a small kon. Comparisons with other ligand-receptor interactions are presented. PMID:19317486

Observation of exchange of micropore water in cement pastes by two-dimensional T(2)-T(2) nuclear magnetic resonance relaxometry.

PubMed

Monteilhet, L; Korb, J-P; Mitchell, J; McDonald, P J

2006-12-01

The first detailed analysis of the two-dimensional (2D) NMR T(2)-T(2) exchange experiment with a period of magnetization storage between the two T(2) relaxation encoding periods (T(2)-store-T(2)) is presented. It is shown that this experiment has certain advantages over the T(1)-T(2) variant for the quantization of chemical exchange. New T(2)-store-T(2) 2D 1H NMR spectra of the pore water within white cement paste are presented. Based on these spectra, the exchange rate of water between the two smallest porosity reservoirs is estimated for the first time. It is found to be of the order of 5 ms{-1}. Further, a careful estimate of the pore sizes of these reservoirs is made. They are found to be of the order of 1.4 nm and 10-30 nm , respectively. A discussion of the results is developed in terms of possible calcium silicate hydrate products. A water diffusion coefficient inferred from the exchange rate and the cement particle size is found to compare favorably with the results of molecular-dynamics simulations to be found in the literature.

Liquid cooled plate heat exchanger for battery cooling of an electric vehicle (EV)

NASA Astrophysics Data System (ADS)

Rahman, M. M.; Rahman, H. Y.; Mahlia, T. M. I.; Sheng, J. L. Y.

2016-03-01

A liquid cooled plate heat exchanger was designed to improve the battery life of an electric vehicle which suffers from premature aging or degradation due to the heat generation during discharging and charging period. Computational fluid dynamics (CFD) was used as a tool to analyse the temperature distribution when a constant surface heat flux was set at the bottom surface of the battery. Several initial and boundary conditions were set based on the past studies on the plate heat exchanger in the simulation software. The design of the plate heat exchanger was based on the Nissan Leaf battery pack to analyse the temperature patterns. Water at different mass flow rates was used as heat transfer fluid. The analysis revealed the designed plate heat exchanger could maintain the surface temperature within the range of 20 to 40°C which is within the safe operating temperature of the battery.

Quantum Scattering Study of Ro-Vibrational Excitations in N+N(sub 2) Collisions under Re-entry Conditions

NASA Technical Reports Server (NTRS)

Wang, Dunyou; Stallcop, James R.; Dateo, Christopher E.; Schwenke, David W.; Huo, Winifred M.

2004-01-01

A three-dimensional time-dependent quantum dynamics approach using a recently developed ab initio potential energy surface is applied to study ro-vibrational excitation in N+N2 exchange scattering for collision energies in the range 2.1- 3.2 eV. State-to-state integral exchange cross sections are examined to determine the distribution of excited rotational states of N(sub 2). The results demonstrate that highly-excited rotational states are produced by exchange scattering and furthermore, that the maximum value of (Delta)j increases rapidly with increasing collision energies. Integral exchange cross sections and exchange rate constants for excitation to the lower (upsilon = 0-3) vibrational energy levels are presented as a function of the collision energy. Excited-vibrational-state distributions for temperatures at 2,000 K and 10,000 K are included.

A novel compact heat exchanger using gap flow mechanism.

PubMed

Liang, J S; Zhang, Y; Wang, D Z; Luo, T P; Ren, T Q

2015-02-01

A novel, compact gap-flow heat exchanger (GFHE) using heat-transfer fluid (HTF) was developed in this paper. The detail design of the GFHE coaxial structure which forms the annular gap passage for HTF is presented. Computational fluid dynamics simulations were introduced into the design to determine the impacts of the gap width and the HTF flow rate on the GFHE performance. A comparative study on the GFHE heating rate, with the gap widths ranged from 0.1 to 1.0 mm and the HTF flow rates ranged from 100 to 500 ml/min, was carried out. Results show that a narrower gap passage and a higher HTF flow rate can yield a higher average heating rate in GFHE. However, considering the compromise between the GFHE heating rate and the HTF pressure drop along the gap, a 0.4 mm gap width is preferred. A testing loop was also set up to experimentally evaluate the GFHE capability. The testing results show that, by using 0.4 mm gap width and 500 ml/min HTF flow rate, the maximum heating rate in the working chamber of the as-made GFHE can reach 18 °C/min, and the average temperature change rates in the heating and cooling processes of the thermal cycle test were recorded as 6.5 and 5.4 °C/min, respectively. These temperature change rates can well satisfy the standard of IEC 60068-2-14:2009 and show that the GFHE developed in this work has sufficient heat exchange capacity and can be used as an ideal compact heat exchanger in small volume desktop thermal fatigue test apparatus.

Internal cycling, not external loading, decides the nutrient limitation in eutrophic lake: A dynamic model with temporal Bayesian hierarchical inference.

PubMed

Wu, Zhen; Liu, Yong; Liang, Zhongyao; Wu, Sifeng; Guo, Huaicheng

2017-06-01

Lake eutrophication is associated with excessive anthropogenic nutrients (mainly nitrogen (N) and phosphorus (P)) and unobserved internal nutrient cycling. Despite the advances in understanding the role of external loadings, the contribution of internal nutrient cycling is still an open question. A dynamic mass-balance model was developed to simulate and measure the contributions of internal cycling and external loading. It was based on the temporal Bayesian Hierarchical Framework (BHM), where we explored the seasonal patterns in the dynamics of nutrient cycling processes and the limitation of N and P on phytoplankton growth in hyper-eutrophic Lake Dianchi, China. The dynamic patterns of the five state variables (Chla, TP, ammonia, nitrate and organic N) were simulated based on the model. Five parameters (algae growth rate, sediment exchange rate of N and P, nitrification rate and denitrification rate) were estimated based on BHM. The model provided a good fit to observations. Our model results highlighted the role of internal cycling of N and P in Lake Dianchi. The internal cycling processes contributed more than external loading to the N and P changes in the water column. Further insights into the nutrient limitation analysis indicated that the sediment exchange of P determined the P limitation. Allowing for the contribution of denitrification to N removal, N was the more limiting nutrient in most of the time, however, P was the more important nutrient for eutrophication management. For Lake Dianchi, it would not be possible to recover solely by reducing the external watershed nutrient load; the mechanisms of internal cycling should also be considered as an approach to inhibit the release of sediments and to enhance denitrification. Copyright © 2017 Elsevier Ltd. All rights reserved.

The role of dynamic surface water-groundwater exchange on streambed denitrification in a first-order, low-relief agricultural watershed

NASA Astrophysics Data System (ADS)

Rahimi, Mina; Essaid, Hedeff I.; Wilson, John T.

2015-12-01

The role of temporally varying surface water-groundwater (SW-GW) exchange on nitrate removal by streambed denitrification was examined along a reach of Leary Weber Ditch (LWD), Indiana, a small, first-order, low-relief agricultural watershed within the Upper Mississippi River basin, using data collected in 2004 and 2005. Stream stage, GW heads (H), and temperatures (T) were continuously monitored in streambed piezometers and stream bank wells for two transects across LWD accompanied by synoptic measurements of stream stage, H, T, and nitrate (NO3) concentrations along the reach. The H and T data were used to develop and calibrate vertical two-dimensional, models of streambed water flow and heat transport across and along the axis of the stream. Model-estimated SW-GW exchange varied seasonally and in response to high-streamflow events due to dynamic interactions between SW stage and GW H. Comparison of 2004 and 2005 conditions showed that small changes in precipitation amount and intensity, evapotranspiration, and/or nearby GW levels within a low-relief watershed can readily impact SW-GW interactions. The calibrated LWD flow models and observed stream and streambed NO3 concentrations were used to predict temporal variations in streambed NO3 removal in response to dynamic SW-GW exchange. NO3 removal rates underwent slow seasonal changes, but also underwent rapid changes in response to high-flow events. These findings suggest that increased temporal variability of SW-GW exchange in low-order, low-relief watersheds may be a factor contributing their more efficient removal of NO3.

The role of dynamic surface water-groundwater exchange on streambed denitrification in a first-order, low-relief agricultural watershed

USGS Publications Warehouse

Rahimi Kazerooni, Mina N.; Essaid, Hedeff I.; Wilson, John T.

2015-01-01

The role of temporally varying surface water-groundwater (SW-GW) exchange on nitrate removal by streambed denitrification was examined along a reach of Leary Weber Ditch (LWD), Indiana, a small, first-order, low-relief agricultural watershed within the Upper Mississippi River basin, using data collected in 2004 and 2005. Stream stage, GW heads (H), and temperatures (T) were continuously monitored in streambed piezometers and stream bank wells for two transects across LWD accompanied by synoptic measurements of stream stage, H, T, and nitrate (NO3) concentrations along the reach. The H and T data were used to develop and calibrate vertical two-dimensional, models of streambed water flow and heat transport across and along the axis of the stream. Model-estimated SW-GW exchange varied seasonally and in response to high-streamflow events due to dynamic interactions between SW stage and GW H. Comparison of 2004 and 2005 conditions showed that small changes in precipitation amount and intensity, evapotranspiration, and/or nearby GW levels within a low-relief watershed can readily impact SW-GW interactions. The calibrated LWD flow models and observed stream and streambed NO3 concentrations were used to predict temporal variations in streambed NO3 removal in response to dynamic SW-GW exchange. NO3 removal rates underwent slow seasonal changes, but also underwent rapid changes in response to high-flow events. These findings suggest that increased temporal variability of SW-GW exchange in low-order, low-relief watersheds may be a factor contributing their more efficient removal of NO3.

Temporal Dynamics of Social Exchange and the Development of Solidarity: "Testing the Waters" versus "Taking a Leap of Faith"

ERIC Educational Resources Information Center

Kuwabara, Ko; Sheldon, Oliver

2012-01-01

In their concerted efforts to unpack the microprocesses that transform repeated exchanges into an exchange relation, exchange theorists have paid little attention to how actors perceive changes and dynamics in exchanges over time. We help fill this gap by studying how temporal patterns of exchange affect the development of cohesion. Some exchange…

Theoretical investigation of exchange and recombination reactions in O(3P)+NO(2Π) collisions

NASA Astrophysics Data System (ADS)

Ivanov, M. V.; Zhu, H.; Schinke, R.

2007-02-01

We present a detailed dynamical study of the kinetics of O(P3)+NO(Π2) collisions including O atom exchange reactions and the recombination of NO2. The classical trajectory calculations are performed on the lowest A'2 and A″2 potential energy surfaces, which were calculated by ab initio methods. The calculated room temperature exchange reaction rate coefficient, kex, is in very good agreement with the measured one. The high-pressure recombination rate coefficient, which is given by the formation rate coefficient and to a good approximation equals 2kex, overestimates the experimental data by merely 20%. The pressure dependence of the recombination rate, kr, is described within the strong-collision model by assigning a stabilization probability to each individual trajectory. The measured falloff curve is well reproduced over five orders of magnitude by a single parameter, i.e., the strong-collision stabilization frequency. The calculations also yield the correct temperature dependence, kr∝T-1.5, of the low-pressure recombination rate coefficient. The dependence of the rate coefficients on the oxygen isotopes are investigated by incorporating the difference of the zero-point energies between the reactant and product NO radicals, ΔZPE, into the potential energy surface. Similar isotope effects as for ozone are predicted for both the exchange reaction and the recombination. Finally, we estimate that the chaperon mechanism is not important for the recombination of NO2, which is in accord with the overall T-1.4 dependence of the measured recombination rate even in the low temperature range.

Adsorption and Exchange Dynamics in Aging Hydroxyethylcellulose Layers on Silica.

PubMed

Mubarekyan; Santore

2000-07-15

The adsorption kinetics of hydroxyethylcellulose (HEC) on silica and relaxations in adsorbed HEC layers were probed using total internal reflectance fluorescence and near-Brewster reflectivity. Like many random-coil polymers, HEC was found to adsorb at the transport-limited rate. Relaxations occurred at nearly constant interfacial mass when HEC layers were exposed to aqueous solvent, causing the subsequent exchange of chains between the layer and the free solution to become increasingly hindered. Eventually, on the time scale of a day, layers became immobilized and unable to accommodate chains from free solution. A continued fluorescence decay, beyond time scales that could be probed with self exchange, suggested further relaxations of the adsorbed HEC. The polydisperse HEC system (with an average molecular weight near 450,000) behaved qualitatively similar to molecular weight standard polyethylene oxide (PEO) layers on silica. For instance, relaxations in PEO layers occurred on a time scale of 10-20 h, like the HEC layers. Young layers of the latter, however, exhibited self-exchange kinetics that were an order of magnitude slower than PEO layers of similar age. This difference in adsorbed layer dynamics was attributed to HEC's stiffer backbone, compared with flexible PEO. Copyright 2000 Academic Press.

Spin-lock imaging of exogenous exchange-based contrast agents to assess tissue pH.

PubMed

Zu, Zhongliang; Li, Hua; Jiang, Xiaoyu; Gore, John C

2018-01-01

Some X-ray contrast agents contain exchangeable protons that give rise to exchange-based effects on MRI, including chemical exchange saturation transfer (CEST). However, CEST has poor specificity to explicit exchange parameters. Spin-lock sequences at high field are also sensitive to chemical exchange. Here, we evaluate whether spin-locking techniques can detect the contrast agent iohexol in vivo after intravenous administration, and their potential for measuring changes in tissue pH. Two metrics of contrast based on R 1ρ , the spin lattice relaxation rate in the rotating frame, were derived from the behavior of R 1ρ at different locking fields. Solutions containing iohexol at different concentrations and pH were used to evaluate the ability of the two metrics to quantify exchange effects. Images were also acquired from rat brains bearing tumors before and after intravenous injections of iohexol to evaluate the potential of spin-lock techniques for detecting the agent and pH variations. The two metrics were found to depend separately on either agent concentration or pH. Spin-lock imaging may therefore provide specific quantification of iohexol concentration and the iohexol-water exchange rate, which reports on pH. Spin-lock techniques may be used to assess the dynamics of intravenous contrast agents and detect extracellular acidification. Magn Reson Med 79:298-305, 2018. © 2017 International Society for Magnetic Resonance in Medicine. © 2017 International Society for Magnetic Resonance in Medicine.

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

PubMed Central

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

2016-01-01

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

Emission of formaldehyde by particleboard : effect of ventilation rate and loading on air-contamination levels

Treesearch

George E. Myers; Muneo Nagaoka

1981-01-01

Dynamic tests for determining the formaldehyde emission behavior of UF-bonded boards involve the measurement of formaldehyde concentration in the air within a vessel which contains a specified board loading L (m2 of board area per m3 of vessel free volume) and is being ventilated at a specified air exchange rate N (hr.-1). Such tests constitute a primary...

Stomata size and spatial pattern effects on leaf gas exchange - a quantitative assessment of plant evolutionary choices

NASA Astrophysics Data System (ADS)

Or, Dani; Assouline, Shmuel; Aminzadeh, Milad; Haghighi, Erfan; Schymanski, Stan; Lehmann, Peter

2014-05-01

Land plants developed a dynamically gas-permeable layer at their leaf surfaces to allow CO2 uptake for photosynthesis while controlling water vapor loss through numerous adjustable openings (stomata) in the impervious leaf epidermis. Details of stomata structure, density and function may vary greatly among different plant families and respond to local environmental conditions, yet they share basic traits in dynamically controlling gaseous exchange rates by varying stomata apertures. We implement a pore scale gas diffusion model to quantitatively interpret the functionality of different combinations of stomata size and pattern on leaf gas exchange and thermal management based on data from fossil records and contemporary data sets. Considering all available data we draw several general conclusions concerning stomata design considerations: (1) the sizes and densities of stomata in the available fossil record leaves were designed to evaporate at rates in the range 0.75≤e/e0 ≤0.99 (relative to free water evaporation); (2) examination of evaporation curves show that for a given stomata size, the density (jointly defining the leaf evaporating area when fully open) was chosen to enable a high sensitivity in reducing evaporation rate with incremental stomatal closure, nevertheless, results show the design includes safety margins to account for different wind conditions (boundary layer thickness); (3) scaled for mean vapor flux, the size of stomata plays a minor role in the uniformity of leaf thermal field for a given stomata density. These principles enable rationale assessment of plant response to raising CO2, and provide a physical framework for considering the consequences of different stomata patterns (patchy) on leaf gas exchange (and thermal regime). In contrast with present quantitative description of traits and functionality of these dynamic covers in terms of gaseous diffusion resistance (or conductance), where stomata size, density and spatial pattern are lumped into a single effective resistance parameter, the present approach enables derivation of nuanced insights and offers predictive capabilities that link changes in stomata structure and geometrical attributes to quantifying environmental influences and feedbacks on leaf structure and function.

Efficiency of Adaptive Temperature-Based Replica Exchange for Sampling Large-Scale Protein Conformational Transitions.

PubMed

Zhang, Weihong; Chen, Jianhan

2013-06-11

Temperature-based replica exchange (RE) is now considered a principal technique for enhanced sampling of protein conformations. It is also recognized that existence of sharp cooperative transitions (such as protein folding/unfolding) can lead to temperature exchange bottlenecks and significantly reduce the sampling efficiency. Here, we revisit two adaptive temperature-based RE protocols, namely, exchange equalization (EE) and current maximization (CM), that were previously examined using atomistic simulations (Lee and Olson, J. Chem. Physics2011, 134, 24111). Both protocols aim to overcome exchange bottlenecks by adaptively adjusting the simulation temperatures, either to achieve uniform exchange rates (in EE) or to maximize temperature diffusion (CM). By designing a realistic yet computationally tractable coarse-grained protein model, one can sample many reversible folding/unfolding transitions using conventional constant temperature molecular dynamics (MD), standard REMD, EE-REMD, and CM-REMD. This allows rigorous evaluation of the sampling efficiency, by directly comparing the rates of folding/unfolding transitions and convergence of various thermodynamic properties of interest. The results demonstrate that both EE and CM can indeed enhance temperature diffusion compared to standard RE, by ∼3- and over 10-fold, respectively. Surprisingly, the rates of reversible folding/unfolding transitions are similar in all three RE protocols. The convergence rates of several key thermodynamic properties, including the folding stability and various 1D and 2D free energy surfaces, are also similar. Therefore, the efficiency of RE protocols does not appear to be limited by temperature diffusion, but by the inherent rates of spontaneous large-scale conformational rearrangements. This is particularly true considering that virtually all RE simulations of proteins in practice involve exchange attempt frequencies (∼ps(-1)) that are several orders of magnitude faster than the slowest protein motions (∼μs(-1)). Our results also suggest that the efficiency of RE will not likely be improved by other protocols that aim to accelerate exchange or temperature diffusion. Instead, protocols with some types of guided tempering will likely be necessary to drive faster large-scale conformational transitions.

Environment-Dependent Guest Exchange in Supramolecular Hosts

PubMed Central

2015-01-01

Dynamic exchange of guest molecules, encapsulated in host assemblies, is a phenomenon in supramolecular chemistry that has important implications in several applications. While the mechanism of exchange in micellar assemblies has been previously investigated, the effect of host and guest environment upon the guest-exchange dynamics has received little attention, if any. In this paper, we study the guest-exchange mechanism in pH-sensitive nanogels along with pH-insensitive nanogels as a control. By systematically comparing the behavior of these nanogels, we show that size, concentration, and hydrophobicity can all play a critical role in guest-exchange dynamics. More importantly, these studies reveal that the dominant mechanism of guest exchange can intimately depend on environmental factors. PMID:25244305

Chaotic examination

NASA Astrophysics Data System (ADS)

Bildirici, Melike; Sonustun, Fulya Ozaksoy; Sonustun, Bahri

2018-01-01

In the regards of chaos theory, new concepts such as complexity, determinism, quantum mechanics, relativity, multiple equilibrium, complexity, (continuously) instability, nonlinearity, heterogeneous agents, irregularity were widely questioned in economics. It is noticed that linear models are insufficient for analyzing unpredictable, irregular and noncyclical oscillations of economies, and for predicting bubbles, financial crisis, business cycles in financial markets. Therefore, economists gave great consequence to use appropriate tools for modelling non-linear dynamical structures and chaotic behaviors of the economies especially in macro and the financial economy. In this paper, we aim to model the chaotic structure of exchange rates (USD-TL and EUR-TL). To determine non-linear patterns of the selected time series, daily returns of the exchange rates were tested by BDS during the period from January 01, 2002 to May 11, 2017 which covers after the era of the 2001 financial crisis. After specifying the non-linear structure of the selected time series, it was aimed to examine the chaotic characteristic for the selected time period by Lyapunov Exponents. The findings verify the existence of the chaotic structure of the exchange rate returns in the analyzed time period.

Modeling of the interest rate policy of the central bank of Russia

NASA Astrophysics Data System (ADS)

Shelomentsev, A. G.; Berg, D. B.; Detkov, A. A.; Rylova, A. P.

2017-11-01

This paper investigates interactions among money supply, exchange rates, inflation, and nominal interest rates, which are regulating parameters of the Central bank policy. The study is based on the data received from Russian source in 2002-2016. The major findings are 1) the interest rate demonstrates almost no relation with inflation; 2) ties of money supply and the nominal interest rate are strong; 3) money supply and inflation show meaningful relations only in comparison to their growth rates. We have developed a dynamic model, which can be used in forecasting of macroeconomic processes.

Dynamic control of photosynthetic photon flux for lettuce production in CELSS

NASA Technical Reports Server (NTRS)

Chun, C.; Mitchell, C. A.

1996-01-01

A new dynamic control of photosynthetic photon flux (PPF) was tested using lettuce canopies growing in the Minitron II plant-growth/canopy gas-exchange system. Canopy photosynthetic rates (Pn) were measured in real time and fedback for further environment control. Pn can be manipulated by changing PPF, which is a good environmental parameter for dynamic control of crop production in a Controlled Ecological Life-Support Systems CELSS. Decision making that combines empirical mathematical models with rule sets developed from recent experimental data was tested. With comparable yield indices and potential for energy savings, dynamic control strategies will contribute greatly to the sustainability of space-deployed CELSS.

Scan-rate and vacuum pressure dependence of the nucleation and growth dynamics in a spin-crossover single crystal: the role of latent heat.

PubMed

Ridier, Karl; Rat, Sylvain; Salmon, Lionel; Nicolazzi, William; Molnár, Gábor; Bousseksou, Azzedine

2018-04-04

Using optical microscopy we studied the vacuum pressure dependence (0.1-1000 mbar) of the nucleation and growth dynamics of the thermally induced first-order spin transition in a single crystal of the spin-crossover compound [Fe(HB(tz)3)2] (tz = 1,2,4-triazol-1-yl). A crossover between a quasi-static hysteresis regime and a temperature-scan-rate-dependent kinetic regime is evidenced around 5 mbar due to the change of the heat exchange coupling between the crystal and its external environment. Remarkably, the absorption/dissipation rate of latent heat was identified as the key factor limiting the switching speed of the crystal.

Ligand lability and chirality inversion in yb heterobimetallic catalysts.

PubMed

Di Bari, Lorenzo; Lelli, Moreno; Salvadori, Piero

2004-09-20

We have investigated the exchange dynamics between the free and bound ligand in K3[Yb[(R)-binol]3], the most active heterobimetallic lanthanoid catalyst for cyclic imine hydrophosphonylation; we found that the Yb-binol bond is labile. The rate constant for this exchange was determined through NMR saturation transfer experiments. Upon addition of (S)-binaphthol, ligand exchange leads to the formation of a small quantity of heterochiral complexes and, in the presence of a molar excess of (S)-binaphthol, to chirality inversion of the whole complex. This demonstrates that, in contrast to other analogous systems, K3[Yb(binol)3] displays a strong chiral discrimination, with the overwhelming preference for ligands of the same configuration. The lability of Yb-binol bond in THF may suggest a ligand-to-substrate exchange as a key step in the catalytic process.

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

Rehman, Nasir, E-mail: nasirzainy1@hotmail.com; Shashiashvili, Malkhaz

The classical Garman-Kohlhagen model for the currency exchange assumes that the domestic and foreign currency risk-free interest rates are constant and the exchange rate follows a log-normal diffusion process.In this paper we consider the general case, when exchange rate evolves according to arbitrary one-dimensional diffusion process with local volatility that is the function of time and the current exchange rate and where the domestic and foreign currency risk-free interest rates may be arbitrary continuous functions of time. First non-trivial problem we encounter in time-dependent case is the continuity in time argument of the value function of the American put optionmore » and the regularity properties of the optimal exercise boundary. We establish these properties based on systematic use of the monotonicity in volatility for the value functions of the American as well as European options with convex payoffs together with the Dynamic Programming Principle and we obtain certain type of comparison result for the value functions and corresponding exercise boundaries for the American puts with different strikes, maturities and volatilities.Starting from the latter fact that the optimal exercise boundary curve is left continuous with right-hand limits we give a mathematically rigorous and transparent derivation of the significant early exercise premium representation for the value function of the American foreign exchange put option as the sum of the European put option value function and the early exercise premium.The proof essentially relies on the particular property of the stochastic integral with respect to arbitrary continuous semimartingale over the predictable subsets of its zeros. We derive from the latter the nonlinear integral equation for the optimal exercise boundary which can be studied by numerical methods.« less

Disparate ultrafast dynamics of itinerant and localized magnetic moments in gadolinium metal

PubMed Central

Frietsch, B.; Bowlan, J.; Carley, R.; Teichmann, M.; Wienholdt, S.; Hinzke, D.; Nowak, U.; Carva, K.; Oppeneer, P. M.; Weinelt, M.

2015-01-01

The Heisenberg–Dirac intra-atomic exchange coupling is responsible for the formation of the atomic spin moment and thus the strongest interaction in magnetism. Therefore, it is generally assumed that intra-atomic exchange leads to a quasi-instantaneous aligning process in the magnetic moment dynamics of spins in separate, on-site atomic orbitals. Following ultrashort optical excitation of gadolinium metal, we concurrently record in photoemission the 4f magnetic linear dichroism and 5d exchange splitting. Their dynamics differ by one order of magnitude, with decay constants of 14 versus 0.8 ps, respectively. Spin dynamics simulations based on an orbital-resolved Heisenberg Hamiltonian combined with first-principles calculations explain the particular dynamics of 5d and 4f spin moments well, and corroborate that the 5d exchange splitting traces closely the 5d spin-moment dynamics. Thus gadolinium shows disparate dynamics of the localized 4f and the itinerant 5d spin moments, demonstrating a breakdown of their intra-atomic exchange alignment on a picosecond timescale. PMID:26355196

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

Dang, Liem X.; Chang, Tsun-Mei

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

Dynamics of radiocesium exchange and interstratification in anhydrous clay interlayers: Bridging the atom and single crystal scales

NASA Astrophysics Data System (ADS)

Lammers, L. N.; Pestana, L. R.; Schaettle, K. B.; Head-Gordon, T.

2016-12-01

High structural charge clay minerals govern the transport and retention of radiocesium in soils and clay-rich geologic repositories. Cation exchange capacities in these phases are typically assumed to be limited to fast-exchanging basal and high-affinity edge sites, while ions in anhydrous interlayers, usually K+, are considered non-exchangeable. However, recent high resolution imaging and spectroscopic studies have demonstrated that Cs ions can in fact exchange with interlayer K without the formation of a hydrated intermediate.1,2 These exchange reactions result in sharp exchange fronts wherein K+ ions are completely replaced by Cs+ at the exchange interface, and the rate of exchange varies from layer to layer, resulting in the formation of interstratified structures (i.e., randomly alternating layers of exchanged and pristine interlayers). Currently, this process cannot be explained by any known exchange mechanism, and consequently, no kinetic expressions are available to account for this phenomenon in models of subsurface radiocesium fate and transport. We present a mesoscale model for direct exchange in anhydrous clay interlayers that is based on the kinetics of single ion migration events. Single atom migration kinetics derived from density functional theory (DFT) calculations are used as inputs to kinetic Monte Carlo (kMC) simulations, which capture the collective dynamics of the exchange process over length- and timescales relevant for implementation in reactive transport models. Potential energy surfaces derived from DFT demonstrate that exchange of Cs+ for K+ in anhydrous interlayers lowers the energy barrier to K ion migration by 145 kJ/mol, leading to a positive feedback mechanism that generates atomically sharp exchange fronts. Our work demonstrates the application of "coarse-graining" techniques to develop models for processes with characteristic length- and timescales not accessible by direct atomistic simulation. 1 Okumura T. et al. (2014) Direct observation of cesium at the interlayer region in phlogopite mica. Microscopy 63(1), 65-72. 2 Fuller A. J. et al. (2015) Caesium incorporation and retention in illite interlayers. Appl. Clay Sci. 108, 128-134.

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

Dang, Liem X.; Schenter, Gregory K.

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

Myosin II Controls Junction Fluctuations to Guide Epithelial Tissue Ordering.

PubMed

Curran, Scott; Strandkvist, Charlotte; Bathmann, Jasper; de Gennes, Marc; Kabla, Alexandre; Salbreux, Guillaume; Baum, Buzz

2017-11-20

Under conditions of homeostasis, dynamic changes in the length of individual adherens junctions (AJs) provide epithelia with the fluidity required to maintain tissue integrity in the face of intrinsic and extrinsic forces. While the contribution of AJ remodeling to developmental morphogenesis has been intensively studied, less is known about AJ dynamics in other circumstances. Here, we study AJ dynamics in an epithelium that undergoes a gradual increase in packing order, without concomitant large-scale changes in tissue size or shape. We find that neighbor exchange events are driven by stochastic fluctuations in junction length, regulated in part by junctional actomyosin. In this context, the developmental increase of isotropic junctional actomyosin reduces the rate of neighbor exchange, contributing to tissue order. We propose a model in which the local variance in tension between junctions determines whether actomyosin-based forces will inhibit or drive the topological transitions that either refine or deform a tissue. Copyright © 2017. Published by Elsevier Inc.

Development of high-productivity, strong cation-exchange adsorbers for protein capture by graft polymerization from membranes with different pore sizes

PubMed Central

Chenette, Heather C.S.; Robinson, Julie R.; Hobley, Eboni; Husson, Scott M.

2012-01-01

This paper describes the surface modification of macroporous membranes using ATRP (atom transfer radical polymerization) to create cation-exchange adsorbers with high protein binding capacity at high product throughput. The work is motivated by the need for a more economical and rapid capture step in downstream processing of protein therapeutics. Membranes with three reported nominal pore sizes (0.2, 0.45, 1.0 μm) were modified with poly(3-sulfopropyl methacrylate, potassium salt) tentacles, to create a high density of protein binding sites. A special formulation was used in which the monomer was protected by a crown ether to enable surface-initiated ATRP of this cationic polyelectrolyte. Success with modification was supported by chemical analysis using Fourier-transform infrared spectroscopy and indirectly by measurement of pure water flux as a function of polymerization time. Uniformity of modification within the membranes was visualized with confocal laser scanning microscopy. Static and dynamic binding capacities were measured using lysozyme protein to allow comparisons with reported performance data for commercial cation-exchange materials. Dynamic binding capacities were measured for flow rates ranging from 13 to 109 column volumes (CV)/min. Results show that this unique ATRP formulation can be used to fabricate cation-exchange membrane adsorbers with dynamic binding capacities as high as 70 mg/mL at a throughput of 100 CV/min and unprecedented productivity of 300 mg/mL/min. PMID:23175597

Conformational exchange of aromatic side chains characterized by L-optimized TROSY-selected ¹³C CPMG relaxation dispersion.

PubMed

Weininger, Ulrich; Respondek, Michal; Akke, Mikael

2012-09-01

Protein dynamics on the millisecond time scale commonly reflect conformational transitions between distinct functional states. NMR relaxation dispersion experiments have provided important insights into biologically relevant dynamics with site-specific resolution, primarily targeting the protein backbone and methyl-bearing side chains. Aromatic side chains represent attractive probes of protein dynamics because they are over-represented in protein binding interfaces, play critical roles in enzyme catalysis, and form an important part of the core. Here we introduce a method to characterize millisecond conformational exchange of aromatic side chains in selectively (13)C labeled proteins by means of longitudinal- and transverse-relaxation optimized CPMG relaxation dispersion. By monitoring (13)C relaxation in a spin-state selective manner, significant sensitivity enhancement can be achieved in terms of both signal intensity and the relative exchange contribution to transverse relaxation. Further signal enhancement results from optimizing the longitudinal relaxation recovery of the covalently attached (1)H spins. We validated the L-TROSY-CPMG experiment by measuring fast folding-unfolding kinetics of the small protein CspB under native conditions. The determined unfolding rate matches perfectly with previous results from stopped-flow kinetics. The CPMG-derived chemical shift differences between the folded and unfolded states are in excellent agreement with those obtained by urea-dependent chemical shift analysis. The present method enables characterization of conformational exchange involving aromatic side chains and should serve as a valuable complement to methods developed for other types of protein side chains.

Do foreign exchange and equity markets co-move in Latin American region? Detrended cross-correlation approach

NASA Astrophysics Data System (ADS)

Bashir, Usman; Yu, Yugang; Hussain, Muntazir; Zebende, Gilney F.

2016-11-01

This paper investigates the dynamics of the relationship between foreign exchange markets and stock markets through time varying co-movements. In this sense, we analyzed the time series monthly of Latin American countries for the period from 1991 to 2015. Furthermore, we apply Granger causality to verify the direction of causality between foreign exchange and stock market and detrended cross-correlation approach (ρDCCA) for any co-movements at different time scales. Our empirical results suggest a positive cross correlation between exchange rate and stock price for all Latin American countries. The findings reveal two clear patterns of correlation. First, Brazil and Argentina have positive correlation in both short and long time frames. Second, the remaining countries are negatively correlated in shorter time scale, gradually moving to positive. This paper contributes to the field in three ways. First, we verified the co-movements of exchange rate and stock prices that were rarely discussed in previous empirical studies. Second, ρDCCA coefficient is a robust and powerful methodology to measure the cross correlation when dealing with non stationarity of time series. Third, most of the studies employed one or two time scales using co-integration and vector autoregressive approaches. Not much is known about the co-movements at varying time scales between foreign exchange and stock markets. ρDCCA coefficient facilitates the understanding of its explanatory depth.

Intermediate disturbance in experimental landscapes improves persistence of beetle metapopulations.

PubMed

Govindan, Byju N; Feng, Zhilan; DeWoody, Yssa D; Swihart, Robert K

2015-03-01

Human-dominated landscapes often feature patches that fluctuate in suitability through space and time, but there is little experimental evidence relating the consequences of dynamic patches for species persistence. We used a spatially and temporally dynamic metapopulation model to assess and compare metapopulation capacity and persistence for red flour beetles (Tribolium castaneum) in experimental landscapes differentiated by resource structure, patch dynamics (destruction and restoration), and connectivity. High connectivity increased the colonization rate of beetles, but this effect was less pronounced in heterogeneous relative to homogeneous landscapes. Higher connectivity and faster patch dynamics increased extinction rates in landscapes. Lower connectivity promoted density-dependent emigration. Heterogeneous landscapes containing patches of different carrying capacity enhanced landscape-level occupancy probability. The highest metapopulation capacity and persistence was observed in landscapes with heterogeneous patches, low connectivity, and slow patch dynamics. Control landscapes with no patch dynamics exhibited rapid declines in abundance and approached extinction due to increased adult mortality in the matrix, higher pupal cannibalism by adults, and extremely low rates of exchange between remaining habitable patches. Our results highlight the role of intermediate patch dynamics, intermediate connectivity, and the nature of density dependence of emigration for persistence of species in heterogeneous landscapes. Our results also demonstrate the importance of incorporating local dynamics into the estimation of metapopulation capacity for conservation planning.

Snohomish RARE project update for Tulalip Tribes | Science ...

EPA Pesticide Factsheets

Rising atmospheric CO2 due to anthropogenic emissions alters local atmospheric gas exchange rates in estuaries, causing alterations of the seawater carbonate system and reductions in pH broadly described as coastal acidification. These changes in marine chemistry have been demonstrated to negatively affect a variety of coastal and estuarine organisms. The naturally dynamic carbonate chemistry of estuaries driven by biological activity, hydrodynamic processes, and intensive biogeochemical cycling has led to uncertainty regarding the role of rising atmospheric CO2 as a driver in these systems, and the suggestion that altered atmospheric exchange may be relatively unimportant to estuarine biogeochemistry. In this presentation, we illustrate how rising atmospheric CO2 from 1765 through 2100 interacts with the observed local carbonate chemistry dynamics of a seagrass bed, and calculated how pHT, pCO2, and Ωaragonite respond. This presentation is part of an informal meeting with the Tulalip Tribes of Tulalip, WA to update them on the progress of the ORD/Region 10 RARE project in the Snohomish estuary to study drivers of coastal acidification. Multiple processes, including primary production and respiration, river runoff, cultural eutrophication, oceanic upwelling, and atmospheric exchange contribute to the characteristically dynamic carbonate conditions in these habitats, with potential interactions amongst these processes leading to coastal acidification. As a

Selective Injection of Magnetization by Slow Chemical Exchange in NMR

NASA Astrophysics Data System (ADS)

Boulat, Benoit; Epstein, David M.; Rance, Mark

1999-06-01

In a system in slow dynamic equilibrium two NMR methods are shown to be suitable for injecting magnetization from one resonance to another by means of slow chemical exchange. The combined outputs of the methods may be employed to measure the value of the off-rate constant κoff in the complex. The methods are implemented experimentally using the complex of molecules composed of the enzyme Esherichia coli dihydrofolate reductase (DHFR) and the ligand folate. In an equilibrium solution with DHFR, folate is known to undergo chemical exchange between a free state and a bound state. The modified synchronous nutation method is applied to a spin of the folate molecule in the free and bound states; magnetization transfer occurs between the two sites due to the underlying exchange process. As a preliminary step for the application of the synchronous nutation method, a new one-dimensional 1H NMR technique is proposed which facilitates the assignment of the resonance of a spin in the bound state, provided the resonance of its exchange partner in the free state is known. This experiment is also used to obtain quantitative estimates of the transverse relaxation rate constant of the bound resonance. The numerical procedure necessary to analyze the experimental results of the synchronous nutation experiment is presented.

Real-time observation of cation exchange kinetics and dynamics at the muscovite-water interface

PubMed Central

Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L.; Sturchio, Neil C.

2017-01-01

Ion exchange at charged solid–liquid interfaces is central to a broad range of chemical and transport phenomena. Real-time observations of adsorption/desorption at the molecular-scale elucidate exchange reaction pathways. Here we report temporal variation in the distribution of Rb+ species at the muscovite (001)–water interface during exchange with Na+. Time-resolved resonant anomalous X-ray reflectivity measurements at 25 °C reveal that Rb+ desorption occurs over several tens of seconds during which thermodynamically stable inner-sphere Rb+ slowly transforms to a less stable outer-sphere Rb+. In contrast, Rb+ adsorption is about twice as fast, proceeding from Rb+ in the bulk solution to the stable inner-sphere species. The Arrhenius plot of the adsorption/desorption rate constants measured from 9 to 55 °C shows that the pre-exponential factor for desorption is significantly smaller than that for adsorption, indicating that this reduced attempt frequency of cation detachment largely explains the slow cation exchange processes at the interface. PMID:28598428

Economic policy optimization based on both one stochastic model and the parametric control theory

NASA Astrophysics Data System (ADS)

Ashimov, Abdykappar; Borovskiy, Yuriy; Onalbekov, Mukhit

2016-06-01

A nonlinear dynamic stochastic general equilibrium model with financial frictions is developed to describe two interacting national economies in the environment of the rest of the world. Parameters of nonlinear model are estimated based on its log-linearization by the Bayesian approach. The nonlinear model is verified by retroprognosis, estimation of stability indicators of mappings specified by the model, and estimation the degree of coincidence for results of internal and external shocks' effects on macroeconomic indicators on the basis of the estimated nonlinear model and its log-linearization. On the base of the nonlinear model, the parametric control problems of economic growth and volatility of macroeconomic indicators of Kazakhstan are formulated and solved for two exchange rate regimes (free floating and managed floating exchange rates)

Amplification of the effects of magnetization exchange by (31) P band inversion for measuring adenosine triphosphate synthesis rates in human skeletal muscle.

PubMed

Ren, Jimin; Sherry, A Dean; Malloy, Craig R

2015-12-01

The goal of this study was to amplify the effects of magnetization exchange between γ-adenosine triphosphate (ATP) and inorganic phosphate (Pi) for evaluation of ATP synthesis rates in human skeletal muscle. The strategy works by simultaneously inverting the (31) P resonances of phosphocreatine (PCr) and ATP using a wide bandwidth, adiabatic inversion radiofrequency pulse followed by observing dynamic changes in intensity of the noninverted Pi signal versus the delay time between the inversion and observation pulses. This band inversion technique significantly delays recovery of γ-ATP magnetization; consequently, the exchange reaction, Pi ↔ γ-ATP, is readily detected and easily analyzed. The ATP synthesis rate measured from high-quality spectral data using this method was 0.073 ± 0.011 s(-1) in resting human skeletal muscle (N = 10). The T1 of Pi was 6.93 ± 1.90 s, consistent with the intrinsic T1 of Pi at this field. The apparent T1 of γ-ATP was 4.07 ± 0.32 s, about two-fold longer than its intrinsic T1 due to storage of magnetization in PCr. Band inversion provides an effective method to amplify the effects of magnetization transfer between γ-ATP and Pi. The resulting data can be easily analyzed to obtain the ATP synthesis rate using a two-site exchange model. © 2014 Wiley Periodicals, Inc.

Trace gas and vegetation feedback responses of Alaskan tussock tundra to long-term snow depth manipulations

NASA Astrophysics Data System (ADS)

Ebbs, L. M.; Taneva, L.; Sullivan, P.; Welker, J. M.

2009-12-01

Changes in the precipitation and temperature regimes in Northern Alaska are manifesting themselves through shifts in sea ice, vegetation traits, animal migration timing and hydrologic dynamics. Changes in precipitation and soil temperature result in changes in plant mineral nutrition, soil nutrient availability, trace gas exchanges and differential nutrient acquisition strategies by arctic plants. In this study, we report on the extent to which long-term increases in snow depth, along with reductions in snow depth alter the magnitudes and pattern of CO2 exchange, soil properties and vegetation traits. A doubling of snow depth (from ~0.5 to ~1.0m) results in a delay of the growing season by ~ 2 weeks, however, by peak season, the rates of CO2 exchange are 50% higher in areas which had experienced deeper snow depth levels. To the contrary, long-term reductions in snow depth results in accelerated rates of plant phenology, however CO2 exchange rates at peak season are 30% less than those areas under ambient snow cover in the preceding winter. Reduced snow depth areas had the coldest winter soil temperatures while the deeper areas had the warmest winter soil temperatures, which may partially explain the summer CO2 fluxes indirectly via different rates of winter N mineralization and differences in leaf N properties. Our results indicate that shifting fall, winter and spring when snow is the primary form of precipitation, may have profound effects on tussock tundra systems.

Ab initio state-specific N2 + O dissociation and exchange modeling for molecular simulations

NASA Astrophysics Data System (ADS)

Luo, Han; Kulakhmetov, Marat; Alexeenko, Alina

2017-02-01

Quasi-classical trajectory (QCT) calculations are used in this work to calculate state-specific N2(X1Σ ) +O(3P ) →2 N(4S ) +O(3P ) dissociation and N2(X1Σ ) +O(3P ) →NO(X2Π ) +N(4S ) exchange cross sections and rates based on the 13A″ and 13A' ab initio potential energy surface by Gamallo et al. [J. Chem. Phys. 119, 2545-2556 (2003)]. The calculations consider translational energies up to 23 eV and temperatures between 1000 K and 20 000 K. Vibrational favoring is observed for dissociation reaction at the whole range of collision energies and for exchange reaction around the dissociation limit. For the same collision energy, cross sections for v = 30 are 4 to 6 times larger than those for the ground state. The exchange reaction has an effective activation energy that is dependent on the initial rovibrational level, which is different from dissociation reaction. In addition, the exchange cross sections have a maximum when the total collision energy (TCE) approaches dissociation energy. The calculations are used to generate compact QCT-derived state-specific dissociation (QCT-SSD) and QCT-derived state-specific exchange (QCT-SSE) models, which describe over 1 × 106 cross sections with about 150 model parameters. The models can be used directly within direct simulation Monte Carlo and computational fluid dynamics simulations. Rate constants predicted by the new models are compared to the experimental measurements, direct QCT calculations and predictions by other models that include: TCE model, Bose-Candler QCT-based exchange model, Macheret-Fridman dissociation model, Macheret's exchange model, and Park's two-temperature model. The new models match QCT-calculated and experimental rates within 30% under nonequilibrium conditions while other models under predict by over an order of magnitude under vibrationally-cold conditions.

Evidence of Large Fluctuations of Stock Return and Financial Crises from Turkey: Using Wavelet Coherency and Varma Modeling to Forecast Stock Return

NASA Astrophysics Data System (ADS)

Oygur, Tunc; Unal, Gazanfer

Shocks, jumps, booms and busts are typical large fluctuation markers which appear in crisis. Models and leading indicators vary according to crisis type in spite of the fact that there are a lot of different models and leading indicators in literature to determine structure of crisis. In this paper, we investigate structure of dynamic correlation of stock return, interest rate, exchange rate and trade balance differences in crisis periods in Turkey over the period between October 1990 and March 2015 by applying wavelet coherency methodologies to determine nature of crises. The time period includes the Turkeys currency and banking crises; US sub-prime mortgage crisis and the European sovereign debt crisis occurred in 1994, 2001, 2008 and 2009, respectively. Empirical results showed that stock return, interest rate, exchange rate and trade balance differences are significantly linked during the financial crises in Turkey. The cross wavelet power, the wavelet coherency, the multiple wavelet coherency and the quadruple wavelet coherency methodologies have been used to examine structure of dynamic correlation. Moreover, in consequence of quadruple and multiple wavelet coherence, strongly correlated large scales indicate linear behavior and, hence VARMA (vector autoregressive moving average) gives better fitting and forecasting performance. In addition, increasing the dimensions of the model for strongly correlated scales leads to more accurate results compared to scalar counterparts.

Partial cooperative unfolding in proteins as observed by hydrogen exchange mass spectrometry

PubMed Central

Engen, John R.; Wales, Thomas E.; Chen, Shugui; Marzluff, Elaine M.; Hassell, Kerry M.; Weis, David D.; Smithgall, Thomas E.

2013-01-01

Many proteins do not exist in a single rigid conformation. Protein motions, or dynamics, exist and in many cases are important for protein function. The analysis of protein dynamics relies on biophysical techniques that can distinguish simultaneously existing populations of molecules and their rates of interconversion. Hydrogen exchange (HX) detected by mass spectrometry (MS) is contributing to our understanding of protein motions by revealing unfolding and dynamics on a wide timescale, ranging from seconds to hours to days. In this review we discuss HX MS-based analyses of protein dynamics, using our studies of multi-domain kinases as examples. Using HX MS, we have successfully probed protein dynamics and unfolding in the isolated SH3, SH2 and kinase domains of the c-Src and Abl kinase families, as well as the role of inter- and intra-molecular interactions in the global control of kinase function. Coupled with high-resolution structural information, HX MS has proved to be a powerful and versatile tool for the analysis of the conformational dynamics in these kinase systems, and has provided fresh insight regarding the regulatory control of these important signaling proteins. HX MS studies of dynamics are applicable not only to the proteins we illustrate here, but to a very wide range of proteins and protein systems, and should play a role in both classification of and greater understanding of the prevalence of protein motion. PMID:23682200

Empirical behavior of a world stock index from intra-day to monthly time scales

NASA Astrophysics Data System (ADS)

Breymann, W.; Lüthi, D. R.; Platen, E.

2009-10-01

Most of the papers that study the distributional and fractal properties of financial instruments focus on stock prices or foreign exchange rates. This typically leads to mixed results concerning the distributions of log-returns and some multi-fractal properties of exchange rates, stock prices, and regional indices. This paper uses a well diversified world stock index as the central object of analysis. Such index approximates the growth optimal portfolio, which is demonstrated under the benchmark approach, it is the ideal reference unit for studying basic securities. When denominating this world index in units of a given currency, one measures the movements of the currency against the entire market. This provides a least disturbed observation of the currency dynamics. In this manner, one can expect to disentangle, e.g., the superposition of the two currencies involved in an exchange rate. This benchmark approach to the empirical analysis of financial data allows us to establish remarkable stylized facts. Most important is the observation that the repeatedly documented multi-fractal appearance of financial time series is very weak and much less pronounced than the deviation of the mono-scaling properties from Brownian-motion type scaling. The generalized Hurst exponent H(2) assumes typical values between 0.55 and 0.6. Accordingly, autocorrelations of log-returns decay according to a power law, and the quadratic variation vanishes when going to vanishing observation time step size. Furthermore, one can identify the Student t distribution as the log-return distribution of a well-diversified world stock index for long time horizons when a long enough data series is used for estimation. The study of dependence properties, finally, reveals that jumps at daily horizon originate primarily in the stock market while at 5min horizon they originate in the foreign exchange market. The principal message of the empirical analysis is that there is evidence that a diffusion model without multi-scaling could reasonably well model the dynamics of a broadly diversified world stock index. in here

Numerical Investigation of Upper-Room UVGI Disinfection Efficacy in an Environmental Chamber with a Ceiling Fan†

PubMed Central

Zhu, Shengwei; Srebric, Jelena; Rudnick, Stephen N.; Vincent, Richard L.; Nardell, Edward A.

2013-01-01

This study investigated the disinfection efficacy of the upper-room ultraviolet germicidal irradiation (UR-UVGI) system with ceiling fans. The investigation used the steady-state Computational Fluid Dynamics (CFD) simulations to solve the rotation of ceiling fan with a rotating reference frame. Two ambient air exchange rates, 2 ACH and 6 ACH (air changes per hour), and four downward fan rotational speeds, 0 rpm, 80 rpm, 150 rpm, and 235 rpm were considered. Additionally, the passive scalar concentration simulations incorporated ultraviolet (UV) dose by two methods: one based on the total exposure time and average UV fluence rate, and another based on SVE3* (New Scale for Ventilation Efficiency 3), originally defined to evaluate the mean age of the air from an air supply opening. Overall, the CFD results enabled the evaluation of UR-UVGI disinfection efficacy using different indices, including the fraction of remaining microorganisms, equivalent air exchange rate, UR-UVGI effectiveness, and tuberculosis infection probability by the Wells-Riley equation. The results indicated that air exchange rate was the decisive factor for determining UR-UVGI performance in disinfecting indoor air. Using a ceiling fan could also improve the performance in general. Furthermore, the results clarified the mechanism for the ceiling fan to influence UR-UVGI disinfection efficacy. PMID:23311354

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

Dang, Liem X.; Chang, Tsun-Mei

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

Currency target-zone modeling: An interplay between physics and economics.

PubMed

Lera, Sandro Claudio; Sornette, Didier

2015-12-01

We study the performance of the euro-Swiss franc exchange rate in the extraordinary period from September 6, 2011 to January 15, 2015 when the Swiss National Bank enforced a minimum exchange rate of 1.20 Swiss francs per euro. Within the general framework built on geometric Brownian motions and based on the analogy between Brownian motion in finance and physics, the first-order effect of such a steric constraint would enter a priori in the form of a repulsive entropic force associated with the paths crossing the barrier that are forbidden. Nonparametric empirical estimates of drift and volatility show that the predicted first-order analogy between economics and physics is incorrect. The clue is to realize that the random-walk nature of financial prices results from the continuous anticipation of traders about future opportunities, whose aggregate actions translate into an approximate efficient market with almost no arbitrage opportunities. With the Swiss National Bank's stated commitment to enforce the barrier, traders' anticipation of this action leads to a vanishing drift together with a volatility of the exchange rate that depends on the distance to the barrier. This effect is described by Krugman's model [P. R. Krugman, Target zones and exchange rate dynamics, Q. J. Econ. 106, 669 (1991)]. We present direct quantitative empirical evidence that Krugman's theoretical model provides an accurate description of the euro-Swiss franc target zone. Motivated by the insights from the economic model, we revise the initial economics-physics analogy and show that, within the context of hindered diffusion, the two systems can be described with the same mathematics after all. Using a recently proposed extended analogy in terms of a colloidal Brownian particle embedded in a fluid of molecules associated with the underlying order book, we derive that, close to the restricting boundary, the dynamics of both systems is described by a stochastic differential equation with a very small constant drift and a linear diffusion coefficient. As a side result, we present a simplified derivation of the linear hydrodynamic diffusion coefficient of a Brownian particle close to a wall.

Rate of disappearance of labeled carbon dioxide from the lungs of humans during breath holding: a method for studying the dynamics of pulmonary CO2 exchange

PubMed Central

Hyde, Richard W.; Puy, Ricardo J. M.; Raub, William F.; Forster, Robert E.

1968-01-01

The dynamics of CO2 exchange in the lungs of man was studied by observing the rate of disappearance of a stable isotope of CO2 (13CO2) from the alveolar gas during breath holding. Over 50% of the inspired isotope disappeared within the first 3 sec followed by a moderately rapid logarithmic decline in which one-half of the remaining 13CO2 disappeared every 10 sec. The large initial disappearance of 13CO2 indicated that alveolar 13CO2 equilibrated in less than 3 sec with the CO2 stored in the pulmonary tissues and capillary blood. The volume of CO2 in the pulmonary tissues calculated from this initial disappearance was 200 ml or 0.33 ml of CO2 per milliliter of pulmonary tissue volume. The alveolar to end-capillary gradient for 13CO2 was calculated by comparing the simultaneous disappearance rates of 13CO2 and acetylene. At rest and during exercise this gradient for 13CO2 was either very small or not discernible, and diffusing capacity for CO2 (DLCO2) exceeded 200 ml/(min × mm Hg). After the administration of a carbonic anhydrase inhibitor the rate of disappearance of 13CO2 decreased markedly. DLCO2 fell to 42 ml/(min × mm Hg) and at least 70% of the exchange of 13CO2 with the CO2 stores in the pulmonary tissues and blood was blocked by the inhibitor. These changes were attributed to impairment of exchange of 13CO2 with the bicarbonate in the pulmonary tissues and blood. The pH of the pulmonary tissues (Vtis) was determined by a method based on the premise that the CO2 space in the pulmonary tissues blocked by the inhibitor represented total bicarbonate content. At an alveolar PCO2 of 40 mm Hg pH of Vtis equalled 6.97 ± 0.09. PMID:5658586

Boundary-layer exchange by bubble: A novel method for generating transient nanofluidic layers

NASA Astrophysics Data System (ADS)

Jennissen, Herbert P.

2005-10-01

Unstirred layers (i.e., Nernst boundary layers) occur on every dynamic solid-liquid interface, constituting a diffusion barrier, since the velocity of a moving liquid approaches zero at the surface (no slip). If a macromolecule-surface reaction rate is higher than the diffusion rate, the Nernst layer is solute depleted and the reaction rate becomes mass-transport limited. The thickness of a Nernst boundary layer (δN) generally lies between 5 and 50μm. In an evanescent wave rheometer, measuring fibrinogen adsorption to fused silica, we made the fundamental observation that an air bubble preceding the sample through the flow cell abolishes the mass-transport limitation of the Nernst diffusion layer. Instead exponential kinetics are found. Experimental and simulation studies strongly indicate that these results are due to the elimination of the Nernst diffusion layer and its replacement by a dynamic nanofluidic layer (δν) maximally 200-300nm thick. It is suggested that the air bubble leads to a transient boundary-layer separation into a novel nanoboundary layer on the surface and the bulk fluid velocity profile separated by a vortex sheet with an estimated lifetime of 30-60s. A bubble-induced boundary-layer exchange from the Nernst to the nanoboundary layer and back is obtained, giving sufficient time for the measurement of unbiased exponential surface kinetics. Noteworthy is that the nanolayer can exist at all and displays properties such as (i) a long persistence and resistance to dissipation by the bulk liquid (boundary-layer-exchange-hysteresis) and (ii) a lack of solute depletion in spite of boundary-layer separation. The boundary-layer-exchange by bubble (BLEB) method therefore appears ideal for enhancing the rates of all types of diffusion-limited macromolecular reactions on surfaces with contact angles between 0° and 90° and only appears limited by slippage due to nanobubbles or an air gap beneath the nanofluidic layer on very hydrophobic surfaces. The possibility of producing nanoboundary layers without any nanostructuring or nanomachining should also be useful for fundamental physical studies in nanofluidics.

Currency target-zone modeling: An interplay between physics and economics

NASA Astrophysics Data System (ADS)

Lera, Sandro Claudio; Sornette, Didier

2015-12-01

We study the performance of the euro-Swiss franc exchange rate in the extraordinary period from September 6, 2011 to January 15, 2015 when the Swiss National Bank enforced a minimum exchange rate of 1.20 Swiss francs per euro. Within the general framework built on geometric Brownian motions and based on the analogy between Brownian motion in finance and physics, the first-order effect of such a steric constraint would enter a priori in the form of a repulsive entropic force associated with the paths crossing the barrier that are forbidden. Nonparametric empirical estimates of drift and volatility show that the predicted first-order analogy between economics and physics is incorrect. The clue is to realize that the random-walk nature of financial prices results from the continuous anticipation of traders about future opportunities, whose aggregate actions translate into an approximate efficient market with almost no arbitrage opportunities. With the Swiss National Bank's stated commitment to enforce the barrier, traders' anticipation of this action leads to a vanishing drift together with a volatility of the exchange rate that depends on the distance to the barrier. This effect is described by Krugman's model [P. R. Krugman, Target zones and exchange rate dynamics, Q. J. Econ. 106, 669 (1991), 10.2307/2937922]. We present direct quantitative empirical evidence that Krugman's theoretical model provides an accurate description of the euro-Swiss franc target zone. Motivated by the insights from the economic model, we revise the initial economics-physics analogy and show that, within the context of hindered diffusion, the two systems can be described with the same mathematics after all. Using a recently proposed extended analogy in terms of a colloidal Brownian particle embedded in a fluid of molecules associated with the underlying order book, we derive that, close to the restricting boundary, the dynamics of both systems is described by a stochastic differential equation with a very small constant drift and a linear diffusion coefficient. As a side result, we present a simplified derivation of the linear hydrodynamic diffusion coefficient of a Brownian particle close to a wall.

Multifractality and heteroscedastic dynamics: An application to time series analysis

NASA Astrophysics Data System (ADS)

Nascimento, C. M.; Júnior, H. B. N.; Jennings, H. D.; Serva, M.; Gleria, Iram; Viswanathan, G. M.

2008-01-01

An increasingly important problem in physics concerns scale invariance symmetry in diverse complex systems, often characterized by heteroscedastic dynamics. We investigate the nature of the relationship between the heteroscedastic and fractal aspects of the dynamics of complex systems, by analyzing the sensitivity to heteroscedasticity of the scaling properties of weakly nonstationary time series. By using multifractal detrended fluctuation analysis, we study the singularity spectra of currency exchange rate fluctuations, after partially or completely eliminating n-point correlations via data shuffling techniques. We conclude that heteroscedasticity can significantly increase multifractality and interpret these findings in the context of self-organizing and adaptive complex systems.

Plant centromere organization: a dynamic structure with conserved functions.

PubMed

Ma, Jianxin; Wing, Rod A; Bennetzen, Jeffrey L; Jackson, Scott A

2007-03-01

Although the structural features of centromeres from most multicellular eukaryotes remain to be characterized, recent analyses of the complete sequences of two centromeric regions of rice, together with data from Arabidopsis thaliana and maize, have illuminated the considerable size variation and sequence divergence of plant centromeres. Despite the severe suppression of meiotic chromosomal exchange in centromeric and pericentromeric regions of rice, the centromere core shows high rates of unequal homologous recombination in the absence of chromosomal exchange, resulting in frequent and extensive DNA rearrangement. Not only is the sequence of centromeric tandem and non-tandem repeats highly variable but also the copy number, spacing, order and orientation, providing ample natural variation as the basis for selection of superior centromere performance. This review article focuses on the structural and evolutionary dynamics of plant centromere organization and the potential molecular mechanisms responsible for the rapid changes of centromeric components.

Application of cinchona-sulfonate-based chiral zwitterionic ion exchangers for the separation of proline-containing dipeptide rotamers and determination of on-column isomerization parameters from dynamic elution profiles.

PubMed

Wernisch, Stefanie; Trapp, Oliver; Lindner, Wolfgang

2013-09-17

The interconversion of cis and trans isomers of dipeptides containing C-terminal proline was studied by dynamic chromatography on zwitterionic chiral stationary phases at temperatures ranging from -15°C to +45°C The cis-trans isomers could be separated below 0°C and above 0-10°C plateau formation and peak coalescence phenomena occurred, which is characteristic for a dynamic process at the time-scale of partitioning. At and above room temperature, full coalescence was observed, which allowed separations of enantiomers without interference from interconversion effects. Analysis of the dynamic elution profiles of the interconverting peptides allowed the determination of isomerization rate constants and thermodynamic activation parameters (isomerization enthalpy, entropy and activation energy). In accordance with established results, isomerization rates and thermodynamic parameters were found to depend on the nature of the N-terminal amino acid. Isomerization barriers were only slightly lower than values determined with other methods but significant differences in the relative contributions of the activation enthalpy and entropy as well as isomerization rates pointed toward selector-moderated isomerization dynamics. Copyright © 2013 Elsevier B.V. All rights reserved.

Dynamers: Polyacylhydrazone reversible covalent polymers, component exchange, and constitutional diversity

PubMed Central

Skene, Williams G.; Lehn, Jean-Marie P.

2004-01-01

Component exchange in reversible polymers allows the generation of dynamic constitutional diversity. The polycondensation of dihydrazides with dialdehydes generates polyacylhydrazones, to which the acylhydrazone functionality formed confers both hydrogen-bonding and reversibility features through the amide and imine groups, respectively. Polyacylhydrazones are thus dynamic polyamides. They are able to reversibly exchange either one or both of their repeating monomer units in the presence of different monomers, thus presenting constitutional dynamic diversity. The polymers subjected to monomer exchange/interchange may be brought to exhibit physical properties vastly different from those of the original polymer. The principle may be extended to other important classes of polymers, giving access, for instance, to dynamic polyureas or polycarbamates. These reversible polymers are therefore able to incorporate, decorporate, or reshuffle their constituting monomers, namely in response to environmental physical or chemical factors, an adaptability feature central to constitutional dynamic chemistry. PMID:15150411

“Invisible” Conformers of an Antifungal Disulfide Protein Revealed by Constrained Cold and Heat Unfolding, CEST-NMR Experiments, and Molecular Dynamics Calculations

PubMed Central

Fizil, Ádám; Gáspári, Zoltán; Barna, Terézia; Marx, Florentine; Batta, Gyula

2015-01-01

Transition between conformational states in proteins is being recognized as a possible key factor of function. In support of this, hidden dynamic NMR structures were detected in several cases up to populations of a few percent. Here, we show by two- and three-state analysis of thermal unfolding, that the population of hidden states may weight 20–40 % at 298 K in a disulfide-rich protein. In addition, sensitive 15N-CEST NMR experiments identified a low populated (0.15 %) state that was in slow exchange with the folded PAF protein. Remarkably, other techniques failed to identify the rest of the NMR “dark matter”. Comparison of the temperature dependence of chemical shifts from experiments and molecular dynamics calculations suggests that hidden conformers of PAF differ in the loop and terminal regions and are most similar in the evolutionary conserved core. Our observations point to the existence of a complex conformational landscape with multiple conformational states in dynamic equilibrium, with diverse exchange rates presumably responsible for the completely hidden nature of a considerable fraction. PMID:25676351

Irrigant flow within a prepared root canal using various flow rates: a Computational Fluid Dynamics study.

PubMed

Boutsioukis, C; Lambrianidis, T; Kastrinakis, E

2009-02-01

To study using computer simulation the effect of irrigant flow rate on the flow pattern within a prepared root canal, during final irrigation with a syringe and needle. Geometrical characteristics of a side-vented endodontic needle and clinically realistic flow rate values were obtained from previous and preliminary studies. A Computational Fluid Dynamics (CFD) model was created using FLUENT 6.2 software. Calculations were carried out for five selected flow rates (0.02-0.79 mL sec(-1)) and velocity and turbulence quantities along the domain were evaluated. Irrigant replacement was limited to 1-1.5 mm apical to the needle tip for all flow rates tested. Low-Reynolds number turbulent flow was detected near the needle outlet. Irrigant flow rate affected significantly the flow pattern within the root canal. Irrigation needles should be placed to within 1 mm from working length to ensure fluid exchange. Turbulent flow of irrigant leads to more efficient irrigant replacement. CFD represents a powerful tool for the study of irrigation.

Statics and dynamics of free and hydrogen-bonded OH groups at the air/water interface.

PubMed

Vila Verde, Ana; Bolhuis, Peter G; Campen, R Kramer

2012-08-09

We use classical atomistic molecular dynamics simulations of two water models (SPC/E and TIP4P/2005) to investigate the orientation and reorientation dynamics of two subpopulations of OH groups belonging to water molecules at the air/water interface at 300 K: those OH groups that donate a hydrogen bond (called "bonded") and those that do not (called "free"). Free interfacial OH groups reorient in two distinct regimes: a fast regime from 0 to 1 ps and a slow regime thereafter. Qualitatively similar behavior was reported by others for free OH groups near extended hydrophobic surfaces. In contrast, the net reorientation of bonded OH groups occurs at a rate similar to that of bulk water. This similarity in reorientation rate results from compensation of two effects: decreasing frequency of hydrogen-bond breaking/formation (i.e., hydrogen-bond exchange) and faster rotation of intact hydrogen bonds. Both changes result from the decrease in density at the air/water interface relative to the bulk. Interestingly, because of the presence of capillary waves, the slowdown of hydrogen-bond exchange is significantly smaller than that reported for water near extended hydrophobic surfaces, but it is almost identical to that reported for water near small hydrophobic solutes. In this sense water at the air/water interface has characteristics of water of hydration of both small and extended hydrophobic solutes.

Probing numerical Laplace inversion methods for two and three-site molecular exchange between interconnected pore structures.

PubMed

Silletta, Emilia V; Franzoni, María B; Monti, Gustavo A; Acosta, Rodolfo H

2018-01-01

Two-dimension (2D) Nuclear Magnetic Resonance relaxometry experiments are a powerful tool extensively used to probe the interaction among different pore structures, mostly in inorganic systems. The analysis of the collected experimental data generally consists of a 2D numerical inversion of time-domain data where T 2 -T 2 maps are generated. Through the years, different algorithms for the numerical inversion have been proposed. In this paper, two different algorithms for numerical inversion are tested and compared under different conditions of exchange dynamics; the method based on Butler-Reeds-Dawson (BRD) algorithm and the fast-iterative shrinkage-thresholding algorithm (FISTA) method. By constructing a theoretical model, the algorithms were tested for a two- and three-site porous media, varying the exchange rates parameters, the pore sizes and the signal to noise ratio. In order to test the methods under realistic experimental conditions, a challenging organic system was chosen. The molecular exchange rates of water confined in hierarchical porous polymeric networks were obtained, for a two- and three-site porous media. Data processed with the BRD method was found to be accurate only under certain conditions of the exchange parameters, while data processed with the FISTA method is precise for all the studied parameters, except when SNR conditions are extreme. Copyright © 2017 Elsevier Inc. All rights reserved.

Nanofiber Ion-Exchange Membranes for the Rapid Uptake and Recovery of Heavy Metals from Water

PubMed Central

Chitpong, Nithinart; Husson, Scott M.

2016-01-01

An evaluation of the performance of polyelectrolyte-modified nanofiber membranes was undertaken to determine their efficacy in the rapid uptake and recovery of heavy metals from impaired waters. The membranes were prepared by grafting poly(acrylic acid) (PAA) and poly(itaconic acid) (PIA) to cellulose nanofiber mats. Performance measurements quantified the dynamic ion-exchange capacity for cadmium (Cd), productivity, and recovery of Cd(II) from the membranes by regeneration. The dynamic binding capacities of Cd(II) on both types of nanofiber membrane were independent of the linear flow velocity, with a residence time of as low as 2 s. Analysis of breakthrough curves indicated that the mass flow rate increased rapidly at constant applied pressure after membranes approached equilibrium load capacity for Cd(II), apparently due to a collapse of the polymer chains on the membrane surface, leading to an increased porosity. This mechanism is supported by hydrodynamic radius (Rh) measurements for PAA and PIA obtained from dynamic light scattering, which show that Rh values decrease upon Cd(II) binding. Volumetric productivity was high for the nanofiber membranes, and reached 0.55 mg Cd/g/min. The use of ethylenediaminetetraacetic acid as regeneration reagent was effective in fully recovering Cd(II) from the membranes. Ion-exchange capacities were constant over five cycles of binding-regeneration. PMID:27999394

Nanofiber Ion-Exchange Membranes for the Rapid Uptake and Recovery of Heavy Metals from Water.

PubMed

Chitpong, Nithinart; Husson, Scott M

2016-12-20

An evaluation of the performance of polyelectrolyte-modified nanofiber membranes was undertaken to determine their efficacy in the rapid uptake and recovery of heavy metals from impaired waters. The membranes were prepared by grafting poly(acrylic acid) (PAA) and poly(itaconic acid) (PIA) to cellulose nanofiber mats. Performance measurements quantified the dynamic ion-exchange capacity for cadmium (Cd), productivity, and recovery of Cd(II) from the membranes by regeneration. The dynamic binding capacities of Cd(II) on both types of nanofiber membrane were independent of the linear flow velocity, with a residence time of as low as 2 s. Analysis of breakthrough curves indicated that the mass flow rate increased rapidly at constant applied pressure after membranes approached equilibrium load capacity for Cd(II), apparently due to a collapse of the polymer chains on the membrane surface, leading to an increased porosity. This mechanism is supported by hydrodynamic radius (R h ) measurements for PAA and PIA obtained from dynamic light scattering, which show that R h values decrease upon Cd(II) binding. Volumetric productivity was high for the nanofiber membranes, and reached 0.55 mg Cd/g/min. The use of ethylenediaminetetraacetic acid as regeneration reagent was effective in fully recovering Cd(II) from the membranes. Ion-exchange capacities were constant over five cycles of binding-regeneration.

Estimation of Hydrogen-Exchange Protection Factors from MD Simulation Based on Amide Hydrogen Bonding Analysis.

PubMed

Park, In-Hee; Venable, John D; Steckler, Caitlin; Cellitti, Susan E; Lesley, Scott A; Spraggon, Glen; Brock, Ansgar

2015-09-28

Hydrogen exchange (HX) studies have provided critical insight into our understanding of protein folding, structure, and dynamics. More recently, hydrogen exchange mass spectrometry (HX-MS) has become a widely applicable tool for HX studies. The interpretation of the wealth of data generated by HX-MS experiments as well as other HX methods would greatly benefit from the availability of exchange predictions derived from structures or models for comparison with experiment. Most reported computational HX modeling studies have employed solvent-accessible-surface-area based metrics in attempts to interpret HX data on the basis of structures or models. In this study, a computational HX-MS prediction method based on classification of the amide hydrogen bonding modes mimicking the local unfolding model is demonstrated. Analysis of the NH bonding configurations from molecular dynamics (MD) simulation snapshots is used to determine partitioning over bonded and nonbonded NH states and is directly mapped into a protection factor (PF) using a logistics growth function. Predicted PFs are then used for calculating deuteration values of peptides and compared with experimental data. Hydrogen exchange MS data for fatty acid synthase thioesterase (FAS-TE) collected for a range of pHs and temperatures was used for detailed evaluation of the approach. High correlation between prediction and experiment for observable fragment peptides is observed in the FAS-TE and additional benchmarking systems that included various apo/holo proteins for which literature data were available. In addition, it is shown that HX modeling can improve experimental resolution through decomposition of in-exchange curves into rate classes, which correlate with prediction from MD. Successful rate class decompositions provide further evidence that the presented approach captures the underlying physical processes correctly at the single residue level. This assessment is further strengthened in a comparison of residue resolved protection factor predictions for staphylococcal nuclease with NMR data, which was also used to compare prediction performance with other algorithms described in the literature. The demonstrated transferable and scalable MD based HX prediction approach adds significantly to the available tools for HX-MS data interpretation based on available structures and models.

Estimation of Hydrogen-Exchange Protection Factors from MD Simulation Based on Amide Hydrogen Bonding Analysis

PubMed Central

Park, In-Hee; Venable, John D.; Steckler, Caitlin; Cellitti, Susan E.; Lesley, Scott A.; Spraggon, Glen; Brock, Ansgar

2015-01-01

Hydrogen exchange (HX) studies have provided critical insight into our understanding of protein folding, structure and dynamics. More recently, Hydrogen Exchange Mass Spectrometry (HX-MS) has become a widely applicable tool for HX studies. The interpretation of the wealth of data generated by HX-MS experiments as well as other HX methods would greatly benefit from the availability of exchange predictions derived from structures or models for comparison with experiment. Most reported computational HX modeling studies have employed solvent-accessible-surface-area based metrics in attempts to interpret HX data on the basis of structures or models. In this study, a computational HX-MS prediction method based on classification of the amide hydrogen bonding modes mimicking the local unfolding model is demonstrated. Analysis of the NH bonding configurations from Molecular Dynamics (MD) simulation snapshots is used to determine partitioning over bonded and non-bonded NH states and is directly mapped into a protection factor (PF) using a logistics growth function. Predicted PFs are then used for calculating deuteration values of peptides and compared with experimental data. Hydrogen exchange MS data for Fatty acid synthase thioesterase (FAS-TE) collected for a range of pHs and temperatures was used for detailed evaluation of the approach. High correlation between prediction and experiment for observable fragment peptides is observed in the FAS-TE and additional benchmarking systems that included various apo/holo proteins for which literature data were available. In addition, it is shown that HX modeling can improve experimental resolution through decomposition of in-exchange curves into rate classes, which correlate with prediction from MD. Successful rate class decompositions provide further evidence that the presented approach captures the underlying physical processes correctly at the single residue level. This assessment is further strengthened in a comparison of residue resolved protection factor predictions for staphylococcal nuclease with NMR data, which was also used to compare prediction performance with other algorithms described in the literature. The demonstrated transferable and scalable MD based HX prediction approach adds significantly to the available tools for HX-MS data interpretation based on available structures and models. PMID:26241692

Correlations of multiscale entropy in the FX market

NASA Astrophysics Data System (ADS)

Stosic, Darko; Stosic, Dusan; Ludermir, Teresa; Stosic, Tatijana

2016-09-01

The regularity of price fluctuations in exchange rates plays a crucial role in FX market dynamics. Distinct variations in regularity arise from economic, social and political events, such as interday trading and financial crisis. This paper applies a multiscale time-dependent entropy method on thirty-three exchange rates to analyze price fluctuations in the FX. Correlation matrices of entropy values, termed entropic correlations, are in turn used to describe global behavior of the market. Empirical results suggest a weakly correlated market with pronounced collective behavior at bi-weekly trends. Correlations arise from cycles of low and high regularity in long-term trends. Eigenvalues of the correlation matrix also indicate a dominant European market, followed by shifting American, Asian, African, and Pacific influences. As a result, we find that entropy is a powerful tool for extracting important information from the FX market.

A Multicontrolled Enamine Configurational Switch Undergoing Dynamic Constitutional Exchange.

PubMed

Ren, Yansong; Svensson, Per H; Ramström, Olof

2018-05-22

A multiresponsive enamine-based molecular switch is presented, in which forward/backward configurational rotation around the C=C bond could be precisely controlled by the addition of an acid/base or metal ions. Fluorescence turn-on/off effects and large Stokes shifts were observed while regulating the switching process with Cu II . The enamine functionality furthermore enabled double dynamic regimes, in which configurational switching could operate in conjunction with constitutional enamine exchange of the rotor part. This behavior was used to construct a prototypical dynamic covalent switch system through enamine exchange with primary amines. The dynamic exchange process could be readily turned on/off by regulating the switch status with pH. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamic Monitoring of Blood-Brain Barrier Integrity using Water Exchange Index (WEI) During Mannitol and CO2 Challenges in Mouse Brain

PubMed Central

Huang, Shuning; Farrar, Christian T.; Dai, Guangping; Kwon, Seon Joo; Bogdanov, Alexei A.; Rosen, Bruce R.; Kim, Young R.

2012-01-01

The integrity of the blood-brain barrier (BBB) is critical to normal brain function. Traditional techniques for assessing BBB disruption rely heavily on the spatiotemporal analysis of extravasating contrast agents. But such methods based on the leakage of relatively large molecules are not suitable to detect subtle BBB impairment or to perform repeated measurements in a short time frame. Quantification of the water exchange rate constant (WER) across the BBB using strictly intravascular contrast agents could provide a much more sensitive method for quantifying the BBB integrity. For estimating the WER, we have recently devised a powerful new method using a water exchange index (WEI) biomarker and demonstrated BBB disruption in an acute stroke model. Here we confirm that the WEI is sensitive to even very subtle changes in the integrity of the BBB caused by (1) systemic hypercapnia and (2) low doses of a hyperosmolar solution. In addition, we have examined the sensitivity and accuracy of the WEI as a biomarker of the WER using computer simulation. In particular, the dependence of the WEI-WER relation on changes in vascular blood volume, T1 relaxation of cellular magnetization, and transcytolemmal water exchange was explored. The simulated WEI was found to vary linearly with the WER for typically encountered exchange rate constants (1–4 Hz) regardless of the blood volume. However, for very high WER (>5 Hz) the WEI became progressively more insensitive to increasing WER. The incorporation of transcytolemmal water exchange, using a three-compartment tissue model, helped to extend the linear WEI regime to slightly higher WER, but had no significant effect for most physiologically important water exchange rate constants (WER<4 Hz). Variation in the cellular T1 had no effect on the WEI. Using both theoretical and experimental approaches, our study validates the utility of the WEI biomarker for monitoring BBB integrity. PMID:23055278

Topology of foreign exchange markets using hierarchical structure methods

NASA Astrophysics Data System (ADS)

Naylor, Michael J.; Rose, Lawrence C.; Moyle, Brendan J.

2007-08-01

This paper uses two physics derived hierarchical techniques, a minimal spanning tree and an ultrametric hierarchical tree, to extract a topological influence map for major currencies from the ultrametric distance matrix for 1995-2001. We find that these two techniques generate a defined and robust scale free network with meaningful taxonomy. The topology is shown to be robust with respect to method, to time horizon and is stable during market crises. This topology, appropriately used, gives a useful guide to determining the underlying economic or regional causal relationships for individual currencies and to understanding the dynamics of exchange rate price determination as part of a complex network.

Near-field excitation exchange between motionless point atoms located near the conductive surface

NASA Astrophysics Data System (ADS)

Kuraptsev, Aleksei S.; Sokolov, Igor M.

2018-04-01

On the basis of quantum microscopic approach we study the excitation dynamics of two motionless point atoms located near the perfectly conducting mirror. We have analyzed the spontaneous decay rate of individual atoms near the mirror as well as the strength of dipole-dipole interaction between different atoms. It is shown that the spontaneous decay rate of an excited atom significantly depends on the distance from this atom to the mirror. In the case when the interatomic separation is less or comparable with the wavelength of resonant radiation, the spontaneous decay dynamics of an excited atom is described by multi-exponential law. It depends both the interatomic separation and the spatial orientation of diatomic quasimolecule.

Ballistic-diffusive approximation for the thermal dynamics of metallic nanoparticles in nanocomposite materials

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

Shirdel-Havar, A. H., E-mail: Amir.hushang.shirdel@gmail.com; Masoudian Saadabad, R.

2015-03-21

Based on ballistic-diffusive approximation, a method is presented to model heat transfer in nanocomposites containing metal nanoparticles. This method provides analytical expression for the temperature dynamics of metallic nanoparticles embedded in a dielectric medium. In this study, nanoparticles are considered as spherical shells, so that Boltzmann equation is solved using ballistic-diffusive approximation to calculate the electron and lattice thermal dynamics in gold nanoparticles, while thermal exchange between the particles is taken into account. The model was used to investigate the influence of particle size and metal concentration of the medium on the electron and lattice thermal dynamics. It is shownmore » that these two parameters are crucial in determining the nanocomposite thermal behavior. Our results showed that the heat transfer rate from nanoparticles to the matrix decreases as the nanoparticle size increases. On the other hand, increasing the metal concentration of the medium can also decrease the heat transfer rate.« less

Modeling Europa's Ice-Ocean Interface

NASA Astrophysics Data System (ADS)

Elsenousy, A.; Vance, S.; Bills, B. G.

2014-12-01

This work focuses on modeling the ice-ocean interface on Jupiter's Moon (Europa); mainly from the standpoint of heat and salt transfer relationship with emphasis on the basal ice growth rate and its implications to Europa's tidal response. Modeling the heat and salt flux at Europa's ice/ocean interface is necessary to understand the dynamics of Europa's ocean and its interaction with the upper ice shell as well as the history of active turbulence at this area. To achieve this goal, we used McPhee et al., 2008 parameterizations on Earth's ice/ocean interface that was developed to meet Europa's ocean dynamics. We varied one parameter at a time to test its influence on both; "h" the basal ice growth rate and on "R" the double diffusion tendency strength. The double diffusion tendency "R" was calculated as the ratio between the interface heat exchange coefficient αh to the interface salt exchange coefficient αs. Our preliminary results showed a strong double diffusion tendency R ~200 at Europa's ice-ocean interface for plausible changes in the heat flux due to onset or elimination of a hydrothermal activity, suggesting supercooling and a strong tendency for forming frazil ice.

Convection-Enhanced Transport into Open Cavities : Effect of Cavity Aspect Ratio.

PubMed

Horner, Marc; Metcalfe, Guy; Ottino, J M

2015-09-01

Recirculating fluid regions occur in the human body both naturally and pathologically. Diffusion is commonly considered the predominant mechanism for mass transport into a recirculating flow region. While this may be true for steady flows, one must also consider the possibility of convective fluid exchange when the outer (free stream) flow is transient. In the case of an open cavity, convective exchange occurs via the formation of lobes at the downstream attachment point of the separating streamline. Previous studies revealed the effect of forcing amplitude and frequency on material transport rates into a square cavity (Horner in J Fluid Mech 452:199-229, 2002). This paper summarizes the effect of cavity aspect ratio on exchange rates. The transport process is characterized using both computational fluid dynamics modeling and dye-advection experiments. Lagrangian analysis of the computed flow field reveals the existence of turnstile lobe transport for this class of flows. Experiments show that material exchange rates do not vary linearly as a function of the cavity aspect ratio (A = W/H). Rather, optima are predicted for A ≈ 2 and A ≈ 2.73, with a minimum occurring at A ≈ 2.5. The minimum occurs at the point where the cavity flow structure bifurcates from a single recirculating flow cell into two corner eddies. These results have significant implications for mass transport environments where the geometry of the flow domain evolves with time, such as coronary stents and growing aneurysms. Indeed, device designers may be able to take advantage of the turnstile-lobe transport mechanism to tailor deposition rates near newly implanted medical devices.

Electrophoretic mobility confirms reassortment bias among geographic isolates of segmented RNA phages

PubMed Central

2013-01-01

Background Sex presents evolutionary costs and benefits, leading to the expectation that the amount of genetic exchange should vary in conditions with contrasting cost-benefit equations. Like eukaryotes, viruses also engage in sex, but the rate of genetic exchange is often assumed to be a relatively invariant property of a particular virus. However, the rates of genetic exchange can vary within one type of virus according to geography, as highlighted by phylogeographic studies of cystoviruses. Here we merge environmental microbiology with experimental evolution to examine sex in a diverse set of cystoviruses, consisting of the bacteriophage ϕ6 and its relatives. To quantify reassortment we manipulated – by experimental evolution – electrophoretic mobility of intact virus particles for use as a phenotypic marker to estimate genetic exchange. Results We generated descendants of ϕ6 that exhibited fast and slow mobility during gel electrophoresis. We identified mutations associated with slow and fast phenotypes using whole genome sequencing and used crosses to establish the production of hybrids of intermediate mobility. We documented natural variation in electrophoretic mobility among environmental isolates of cystoviruses and used crosses against a common fast mobility ϕ6 strain to monitor the production of hybrids with intermediate mobility, thus estimating the amount of genetic exchange. Cystoviruses from different geographic locations have very different reassortment rates when measured against ϕ6, with viruses isolated from California showing higher reassortment rates than those from the Northeastern US. Conclusions The results confirm that cystoviruses from different geographic locations have remarkably different reassortment rates –despite similar genome structure and replication mechanisms– and that these differences are in large part due to sexual reproduction. This suggests that particular viruses may indeed exhibit diverse sexual behavior, but wide geographic sampling, across varying environmental conditions may be necessary to characterize the full repertoire. Variation in reassortment rates can assist in the delineation of viral populations and is likely to provide insight into important viral evolutionary dynamics including the rate of coinfection, virulence, and host range shifts. Electrophoretic mobility may be an indicator of important determinants of fitness and the techniques herein can be applied to the study of other viruses. PMID:24059872

On exchange rate misalignments in the Eurozone's peripheral countries

NASA Astrophysics Data System (ADS)

Grochová, Ladislava; Plecitá, Klára

2013-10-01

In this paper we model equilibrium exchange rates for the Eurozone's countries on the basis of the Behavioural Equilibrium Exchange Rate approach, which assumes, that equilibrium exchange rates are in the long run affected by economic fundamentals. To assess the degree of exchange rate misalignment for the Eurozone's peripheral countries - Portugal, Ireland, Greece and Spain - the gap between the actual and the modelled equilibrium exchange rate value is calculated. Our results show that Spain, Portugal and Ireland had their real exchange rates in equilibrium when they joined the Eurozone; however their real exchange rates have been persistently overvalued since the beginning of the 2000s. Greece, on the other hand, has experienced diminishing undervaluation at the beginning of its membership in the Eurozone and since 2009 has exhibited an overvalued real exchange rate.

Some potential errors in the measurement of mercury gas exchange at the soil surface using a dynamic flux chamber.

PubMed

Gillis, A; Miller, D R

2000-10-09

A series of controlled environment experiments were conducted to examine the use of a dynamic flux chamber to measure soil emission and absorption of total gaseous mercury (TGM). Uncertainty about the appropriate airflow rates through the chamber and chamber exposure to ambient wind are shown to be major sources of potential error. Soil surface mercury flux measurements over a range of chamber airflow rates showed a positive linear relationship between flux rates and airflow rate through the chamber. Mercury flux measurements using the chamber in an environmental wind tunnel showed that exposure of the system to ambient winds decreased the measured flux rates by 40% at a wind speed of 1.0 m s(-1) and 90% at a wind speed of 2 m s(-1). Wind tunnel measurements also showed that the chamber footprint was limited to the area of soil inside the chamber and there is little uncertainty of the footprint size in dry soil.

Ultrafast atomic layer-by-layer oxygen vacancy-exchange diffusion in double-perovskite LnBaCo2O5.5+δ thin films.

PubMed

Bao, Shanyong; Ma, Chunrui; Chen, Garry; Xu, Xing; Enriquez, Erik; Chen, Chonglin; Zhang, Yamei; Bettis, Jerry L; Whangbo, Myung-Hwan; Dong, Chuang; Zhang, Qingyu

2014-04-22

Surface exchange and oxygen vacancy diffusion dynamics were studied in double-perovskites LnBaCo2O5.5+δ (LnBCO) single-crystalline thin films (Ln = Er, Pr; -0.5 < δ < 0.5) by carefully monitoring the resistance changes under a switching flow of oxidizing gas (O2) and reducing gas (H2) in the temperature range of 250 ~ 800 °C. A giant resistance change ΔR by three to four orders of magnitude in less than 0.1 s was found with a fast oscillation behavior in the resistance change rates in the ΔR vs. t plots, suggesting that the oxygen vacancy exchange diffusion with oxygen/hydrogen atoms in the LnBCO thin films is taking the layer by layer oxygen-vacancy-exchange mechanism. The first principles density functional theory calculations indicate that hydrogen atoms are present in LnBCO as bound to oxygen forming O-H bonds. This unprecedented oscillation phenomenon provides the first direct experimental evidence of the layer by layer oxygen vacancy exchange diffusion mechanism.

Real-time observation of cation exchange kinetics and dynamics at the muscovite-water interface

DOE PAGES

Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L.; ...

2017-06-09

Here, ion exchange at charged solid–liquid interfaces is central to a broad range of chemical and transport phenomena. Real-time observations of adsorption/desorption at the molecular-scale elucidate exchange reaction pathways. Here, we report temporal variation in the distribution of Rb + species at the muscovite (001)–water interface during exchange with Na +. Time-resolved resonant anomalous X-ray reflectivity measurements reveal that Rb + desorption occurs over several tens of seconds during which thermodynamically stable inner-sphere Rb + slowly transforms to less stable outer-sphere Rb + at 25°C. In contrast, Rb + adsorption is about twice as fast, proceeding quickly from Rb +more » in the bulk solution to the stable inner-sphere species. The Arrhenius plot of the adsorption/desorption rate constants measured from 9 to 55°C shows that the pre-exponential factor for desorption is significantly smaller than for adsorption, indicating that this reduced attempt frequency of cation detachment largely explains the slow cation exchange processes at the interface.« less

Detecting a currency's dominance or dependence using foreign exchange network trees

NASA Astrophysics Data System (ADS)

McDonald, Mark; Suleman, Omer; Williams, Stacy; Howison, Sam; Johnson, Neil F.

2005-10-01

In a system containing a large number of interacting stochastic processes, there will typically be many nonzero correlation coefficients. This makes it difficult to either visualize the system’s interdependencies, or identify its dominant elements. Such a situation arises in foreign exchange (FX), which is the world’s biggest market. Here we develop a network analysis of these correlations using minimum spanning trees (MSTs). We show that not only do the MSTs provide a meaningful representation of the global FX dynamics, but they also enable one to determine momentarily dominant and dependent currencies. We find that information about a country’s geographical ties emerges from the raw exchange-rate data. Most importantly from a trading perspective, we discuss how to infer which currencies are “in play” during a particular period of time.

Dynamic subcellular partitioning of the nucleolar transcription factor TIF-IA under ribotoxic stress.

PubMed

Szymański, Jedrzej; Mayer, Christine; Hoffmann-Rohrer, Urs; Kalla, Claudia; Grummt, Ingrid; Weiss, Matthias

2009-07-01

TIF-IA is a basal transcription factor of RNA polymerase I (Pol I) that is a major target of the JNK2 signaling pathway in response to ribotoxic stress. Using advanced fluorescence microscopy and kinetic modeling we elucidated the subcellular localization of TIF-IA and its exchange dynamics between the nucleolus, nucleoplasm and cytoplasm upon ribotoxic stress. In steady state, the majority of (GFP-tagged) TIF-IA was in the cytoplasm and the nucleus, a minor portion (7%) localizing to the nucleoli. We observed a rapid shuttling of GFP-TIF-IA between the different cellular compartments with a mean residence time of approximately 130 s in the nucleus and only approximately 30 s in the nucleoli. The import rate from the cytoplasm to the nucleus was approximately 3-fold larger than the export rate, suggesting an importin/exportin-mediated transport rather than a passive diffusion. Upon ribotoxic stress, GFP-TIF-IA was released from the nucleoli with a half-time of approximately 24 min. Oxidative stress and inhibition of protein synthesis led to a relocation of GFP-TIF-IA with slower kinetics while osmotic stress had no effect. The observed relocation was much slower than the nucleo-cytoplasmic and nucleus-nucleolus exchange rates of GFP-TIF-IA, indicating a time-limiting step upstream of the JNK2 pathway. In support of this, time-course experiments on the activity of JNK2 revealed the activation of the JNK kinase as the rate-limiting step.

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

NASA Astrophysics Data System (ADS)

Chang, Tsun-Mei; Dang, Liem X.

2017-10-01

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

Characterization of cross-linked cellulosic ion-exchange adsorbents: 2. Protein sorption and transport.

PubMed

Angelo, James M; Cvetkovic, Aleksandar; Gantier, Rene; Lenhoff, Abraham M

2016-03-18

Adsorption behavior in the HyperCel family of cellulosic ion-exchange materials (Pall Corporation) was characterized using methods to assess, quantitatively and qualitatively, the dynamics of protein uptake as well as static adsorption as a function of ionic strength and protein concentration using several model proteins. The three exchangers studied all presented relatively high adsorptive capacities under low ionic strength conditions, comparable to commercially available resins containing polymer functionalization aimed at increasing that particular characteristic. The strong cation- and anion-exchange moieties showed higher sensitivity to increasing salt concentrations, but protein affinity on the salt-tolerant STAR AX HyperCel exchanger remained strong at ionic strengths normally used in downstream processing to elute material fully during ion-exchange chromatography. Very high uptake rates were observed in both batch kinetics experiments and time-series confocal laser scanning microscopy, suggesting low intraparticle transport resistances relative to external film resistance, even at higher bulk protein concentrations where the opposite is typically observed. Electron microscopy imaging of protein adsorbed phases provided additional insight into particle structure that could not be resolved in previous work on the bare resins. Copyright © 2016 Elsevier B.V. All rights reserved.

Cell membrane water exchange effects in prostate DCE-MRI

NASA Astrophysics Data System (ADS)

Li, Xin; Priest, Ryan A.; Woodward, William J.; Siddiqui, Faisal; Beer, Tomasz M.; Garzotto, Mark G.; Rooney, William D.; Springer, Charles S.

2012-05-01

Prostate Dynamic-Contrast-Enhanced (DCE) MRI often exhibits fast and extensive global contrast reagent (CR) extravasation - measured by Ktrans, a pharmacokinetic parameter proportional to its rate. This implies that the CR concentration [CR] is high in the extracellular, extravascular space (EES) during a large portion of the DCE-MRI study. Since CR is detected indirectly, through water proton signal change, the effects of equilibrium transcytolemmal water exchange may be significant in the data and thus should be admitted in DCE-MRI pharmacokinetic modeling. The implications for parameter values were investigated through simulations, and analyses of actual prostate data, with different models. Model parameter correlation and precision were also explored. A near-optimal version of the exchange-sensitized model was found. Our results indicate that ΔKtrans (the Ktrans difference returned by this version and a model assuming exchange to be effectively infinitely fast) may be a very useful biomarker for discriminating malignant from benign prostate tissue. Using an exchange-sensitized model, we find that the mean intracellular water lifetime (τi) - an exchange measure - can be meaningfully mapped for the prostate. Our results show prostate glandular zone differences in τi values.

Ion Exchange Technology Development in Support of the Urine Processor Assembly Precipitation Prevention Project for the International Space Station

NASA Technical Reports Server (NTRS)

Mitchell, Julie L.; Broyan, James L.; Pickering, Karen D.; Adam, Niklas; Casteel, Michael; Callahan, Michael; Carrier, Chris

2012-01-01

In support of the Urine Processor Assembly Precipitation Prevention Project (UPA PPP), multiple technologies were explored to prevent CaSO4 2H2O (gypsum) precipitation during the on-orbit distillation process. Gypsum precipitation currently limits the water recovery rate onboard the International Space Station (ISS) to 70% versus the planned 85% target water recovery rate. Due to its ability to remove calcium cations in pretreated augmented urine (PTAU), ion exchange was selected as one of the technologies for further development by the PPP team. A total of 13 ion exchange resins were evaluated in various equilibrium and dynamic column tests with solutions of dissolved gypsum, urine ersatz, PTAU, and PTAU brine at 85% water recovery. While initial evaluations indicated that the Purolite SST60 resin had the highest calcium capacity in PTAU (0.30 meq/mL average), later tests showed that the Dowex G26 and Amberlite FPC12H resins had the highest capacity (0.5 meq/mL average). Testing at the Marshall Spaceflight Center (MSFC) integrates the ion exchange technology with a UPA ground article under flight-like pulsed flow conditions with PTAU. To date, no gypsum precipitation has taken place in any of the initial evaluations.

Modeling of the Bosphorus exchange flow dynamics

NASA Astrophysics Data System (ADS)

Sözer, Adil; Özsoy, Emin

2017-04-01

The fundamental hydrodynamic behavior of the Bosphorus Strait is investigated through a numerical modeling study using alternative configurations of idealized or realistic geometry. Strait geometry and basin stratification conditions allow for hydraulic controls and are ideally suited to support the maximal-exchange regime, which determines the rate of exchange of waters originating from the adjacent Black and Mediterranean Seas for a given net transport. Steady-state hydraulic controls are demonstrated by densimetric Froude number calculations under layered flow approximations when corrections are applied to account for high velocity shears typically observed in the Bosphorus. Analyses of the model results reveal many observed features of the strait, including critical transitions at hydraulic controls and dissipation by turbulence and hydraulic jumps. It is found that the solution depends on initialization, especially with respect to the basin initial conditions. Significant differences between the controlled maximal-exchange and drowned solutions suggest that a detailed modeling implementation involving coupling with adjacent basins needs to take full account of the Bosphorus Strait in terms of the physical processes to be resolved.

Chair interconversion and reactivity of mannuronic acid esters.

PubMed

Rönnols, Jerk; Walvoort, Marthe T C; van der Marel, Gijsbert A; Codée, Jeroen D C; Widmalm, Göran

2013-12-14

Mannopyranosyluronic acids display a very unusual conformation behavior in that they often prefer to adopt a (1)C4 chair conformation. They are endowed with a strikingly high reactivity when used in a glycosylation reaction as a glycosyl donor. To investigate the unusual conformational behavior a series of mannuronic acid ester derivatives, comprising anomeric triflate species and O-methyl glycosides, was examined by dynamic NMR experiments, through lineshape analysis of (1)H and (19)F NMR spectra at various temperatures from -80 °C to 0 °C. Exchange rates between (4)C1 and (1)C4 chair conformations were found to depend on the electronic properties and the size of the C2 substituent (F, N3 or OBn) and the aglycon, with higher exchange rates for the glycosyl triflates and smaller C2 substituents. Low temperature (19)F exchange spectroscopy experiments showed that the covalently bound anomeric triflates did not exchange with free triflate species present in the reaction mixture. To relate the conformational behavior of the intermediate triflates to their reactivity in a glycosylation reaction, their relative reactivity was determined via competition reactions monitored by (1)H NMR spectroscopy at low temperature. The 2-O-benzyl ether compound was found to be most reactive whereas the 2-fluoro compound - the most flexible of the studied compounds - was least reactive. Whereas the ring-flip of the mannuronic acids is important for the enhanced reactivity of the donors, the rate of the ring-flip has little influence on the relative reactivity.

Improved protein hydrogen/deuterium exchange mass spectrometry platform with fully automated data processing.

PubMed

Zhang, Zhongqi; Zhang, Aming; Xiao, Gang

2012-06-05

Protein hydrogen/deuterium exchange (HDX) followed by protease digestion and mass spectrometric (MS) analysis is accepted as a standard method for studying protein conformation and conformational dynamics. In this article, an improved HDX MS platform with fully automated data processing is described. The platform significantly reduces systematic and random errors in the measurement by introducing two types of corrections in HDX data analysis. First, a mixture of short peptides with fast HDX rates is introduced as internal standards to adjust the variations in the extent of back exchange from run to run. Second, a designed unique peptide (PPPI) with slow intrinsic HDX rate is employed as another internal standard to reflect the possible differences in protein intrinsic HDX rates when protein conformations at different solution conditions are compared. HDX data processing is achieved with a comprehensive HDX model to simulate the deuterium labeling and back exchange process. The HDX model is implemented into the in-house developed software MassAnalyzer and enables fully unattended analysis of the entire protein HDX MS data set starting from ion detection and peptide identification to final processed HDX output, typically within 1 day. The final output of the automated data processing is a set (or the average) of the most possible protection factors for each backbone amide hydrogen. The utility of the HDX MS platform is demonstrated by exploring the conformational transition of a monoclonal antibody by increasing concentrations of guanidine.

Gas-Phase Hydrogen-Deuterium Exchange Labeling of Select Peptide Ion Conformer Types: a Per-Residue Kinetics Analysis.

PubMed

Khakinejad, Mahdiar; Kondalaji, Samaneh Ghassabi; Tafreshian, Amirmahdi; Valentine, Stephen J

2015-07-01

The per-residue, gas-phase hydrogen deuterium exchange (HDX) kinetics for individual amino acid residues on selected ion conformer types of the model peptide KKDDDDDIIKIIK have been examined using ion mobility spectrometry (IMS) and HDX-tandem mass spectrometry (MS/MS) techniques. The [M + 4H](4+) ions exhibit two major conformer types with collision cross sections of 418 Å(2) and 446 Å(2); the [M + 3H](3+) ions also yield two different conformer types having collision cross sections of 340 Å(2) and 367 Å(2). Kinetics plots of HDX for individual amino acid residues reveal fast- and slow-exchanging hydrogens. The contributions of each amino acid residue to the overall conformer type rate constant have been estimated. For this peptide, N- and C-terminal K residues exhibit the greatest contributions for all ion conformer types. Interior D and I residues show decreased contributions. Several charge state trends are observed. On average, the D residues of the [M + 3H](3+) ions show faster HDX rate contributions compared with [M + 4H](4+) ions. In contrast the interior I8 and I9 residues show increased accessibility to exchange for the more elongated [M + 4H](4+) ion conformer type. The contribution of each residue to the overall uptake rate showed a good correlation with a residue hydrogen accessibility score model calculated using a distance from charge site and initial incorporation site for nominal structures obtained from molecular dynamic simulations (MDS).

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

PubMed

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

2008-11-06

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

Compositional changes of minerals associated with dynamic recrystallizatin

NASA Astrophysics Data System (ADS)

Yund, Richard A.; Tullis, Jan

1991-09-01

The rate of compositional and isotopic exchange between minerals may be enhanced significantly if the rock is deformed simultaneously. The enhanced exchange rate may result from a reduction in grain size (shorter distance for volume diffusion), dissolution and growth of grains by diffusion creep (pressure solution), or the movement of high-angle grain boundaries through strained grains during recrystallization in the dislocation creep regime. The migration of high-angle grain boundaries provides high diffusivity paths for the rapid exchange of components during recrystallization. The operation of the latter process has been demonstrated by deforming aggregates consisting of two plagioclases (An1 and An79) at 900°C, 1 GPa confining pressure, and a strain rate of ˜2x10-6s-1. The polygonal, recrystallized grains were analyzed using an analytical transmission electron microscope and have a variable but often intermediate composition. At the conditions of these experiments, the volume interdiffusion rate of NaSi/CaAl is too slow to produce any observable chemical change, and microstructural-chemical relations indicate that the contribution from diffusion creep was insignificant except for initially fine-grained (2 10 μm) aggregates. These results indicate that strain-induced recrystallization can be an effective mechanism for enhancing the kinetics of metamorphic reactions and for resetting the isotope systematics of minerals such as feldspars, pyroxenes, and amphiboles.

Coupled acoustic-gravity field for dynamic evaluation of ion exchange with a single resin bead.

PubMed

Kanazaki, Takahiro; Hirawa, Shungo; Harada, Makoto; Okada, Tetsuo

2010-06-01

A coupled acoustic-gravity field is efficient for entrapping a particle at the position determined by its acoustic properties rather than its size. This field has been applied to the dynamic observation of ion-exchange reactions occurring in a single resin bead. The replacement of counterions in an ion-exchange resin induces changes in its acoustic properties, such as density and compressibility. Therefore, we can visually trace the advancement of an ion-exchange reaction as a time change in the levitation position of a resin bead entrapped in the field. Cation-exchange reactions occurring in resin beads with diameters of 40-120 microm are typically completed within 100-200 s. Ion-exchange equilibrium or kinetics is often evaluated with off-line chemical analyses, which require a batch amount of ion exchangers. Measurements with a single resin particle allow us to evaluate ion-exchange dynamics and kinetics of ions including those that are difficult to measure by usual off-line analyses. The diffusion properties of ions in resins have been successfully evaluated from the time change in the levitation positions of resin beads.

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

PubMed Central

2015-01-01

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

High-field Overhauser dynamic nuclear polarization in silicon below the metal-insulator transition.

PubMed

Dementyev, Anatoly E; Cory, David G; Ramanathan, Chandrasekhar

2011-04-21

Single crystal silicon is an excellent system to explore dynamic nuclear polarization (DNP), as it exhibits a continuum of properties from metallic to insulating as a function of doping concentration and temperature. At low doping concentrations DNP has been observed to occur via the solid effect, while at very high-doping concentrations an Overhauser mechanism is responsible. Here we report the hyperpolarization of (29)Si in n-doped silicon crystals, with doping concentrations in the range of (1-3) × 10(17) cm(-3). In this regime exchange interactions between donors become extremely important. The sign of the enhancement in our experiments and its frequency dependence suggest that the (29)Si spins are directly polarized by donor electrons via an Overhauser mechanism within exchange-coupled donor clusters. The exchange interaction between donors only needs to be larger than the silicon hyperfine interaction (typically much smaller than the donor hyperfine coupling) to enable this Overhauser mechanism. Nuclear polarization enhancement is observed for a range of donor clusters in which the exchange energy is comparable to the donor hyperfine interaction. The DNP dynamics are characterized by a single exponential time constant that depends on the microwave power, indicating that the Overhauser mechanism is a rate-limiting step. Since only about 2% of the silicon nuclei are located within 1 Bohr radius of the donor electron, nuclear spin diffusion is important in transferring the polarization to all the spins. However, the spin-diffusion time is much shorter than the Overhauser time due to the relatively weak silicon hyperfine coupling strength. In a 2.35 T magnetic field at 1.1 K, we observed a DNP enhancement of 244 ± 84 resulting in a silicon polarization of 10.4 ± 3.4% following 2 h of microwave irradiation.

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

PubMed

Huang, Kun; García, Angel E

2014-10-14

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

DYNACLIPS (DYNAmic CLIPS): A dynamic knowledge exchange tool for intelligent agents

NASA Technical Reports Server (NTRS)

Cengeloglu, Yilmaz; Khajenoori, Soheil; Linton, Darrell

1994-01-01

In a dynamic environment, intelligent agents must be responsive to unanticipated conditions. When such conditions occur, an intelligent agent may have to stop a previously planned and scheduled course of actions and replan, reschedule, start new activities and initiate a new problem solving process to successfully respond to the new conditions. Problems occur when an intelligent agent does not have enough knowledge to properly respond to the new situation. DYNACLIPS is an implementation of a framework for dynamic knowledge exchange among intelligent agents. Each intelligent agent is a CLIPS shell and runs a separate process under SunOS operating system. Intelligent agents can exchange facts, rules, and CLIPS commands at run time. Knowledge exchange among intelligent agents at run times does not effect execution of either sender and receiver intelligent agent. Intelligent agents can keep the knowledge temporarily or permanently. In other words, knowledge exchange among intelligent agents would allow for a form of learning to be accomplished.

Going Places: Exploring the Impact of Intra-Sectoral Mobility on Research Productivity and Communication Behaviors in Japanese Academia

ERIC Educational Resources Information Center

Horta, Hugo; Yonezawa, Akiyoshi

2013-01-01

This study analyzes the impact of intra-sectoral mobility of academics on research productivity and R&D information exchange dynamics in Japan. The analysis shows intra-sectoral mobility impacting positively both research productivity and information exchange dynamics, but that this effect--except for information exchange with peers based…

Modeling and Simulation of A Microchannel Cooling System for Vitrification of Cells and Tissues.

PubMed

Wang, Y; Zhou, X M; Jiang, C J; Yu, Y T

The microchannel heat exchange system has several advantages and can be used to enhance heat transfer for vitrification. To evaluate the microchannel cooling method and to analyze the effects of key parameters such as channel structure, flow rate and sample size. A computational flow dynamics model is applied to study the two-phase flow in microchannels and its related heat transfer process. The fluid-solid coupling problem is solved with a whole field solution method (i.e., flow profile in channels and temperature distribution in the system being simulated simultaneously). Simulation indicates that a cooling rate >10 4 C/min is easily achievable using the microchannel method with the high flow rate for a board range of sample sizes. Channel size and material used have significant impact on cooling performance. Computational flow dynamics is useful for optimizing the design and operation of the microchannel system.

Turbulent cascades in foreign exchange markets

NASA Astrophysics Data System (ADS)

Ghashghaie, S.; Breymann, W.; Peinke, J.; Talkner, P.; Dodge, Y.

1996-06-01

THE availability of high-frequency data for financial markets has made it possible to study market dynamics on timescales of less than a day1. For foreign exchange (FX) rates Müller et al.2 have shown that there is a net flow of information from long to short timescales: the behaviour of long-term traders (who watch the markets only from time to time) influences the behaviour of short-term traders (who watch the markets continuously). Motivated by this hierarchical feature, we have studied FX market dynamics in more detail, and report here an analogy between these dynamics and hydrodynamic turbulence3-8. Specifically, the relationship between the probability density of FX price changes (δx) and the time delay (δt) (Fig. la) is much the same as the relationship between the probability density of the velocity differences (δv) of two points in a turbulent flow and their spatial separation δr (Fig. 1b). Guided by this similarity we claim that there is an information cascade in FX market dynamics that corresponds to the energy cascade in hydrodynamic turbulence. On the basis of this analogy we can now rationalize the statistics of FX price differences at different time delays, which is important for, for example, option pricing. The analogy also provides a conceptual framework for understanding the short-term dynamics of speculative markets.

Nanoscale cluster dynamics in the martensitic phase of Ni-Mn-Sn shape-memory alloys

NASA Astrophysics Data System (ADS)

Hoch, Michael; Yuan, Shaojie; Kuhns, Phillip; Reyes, Arneil; Brooks, James; Phelan, Daniel; Srivastava, Vijay; James, Richard; Leighton, Chris

2015-03-01

The martensitic phases of Ni-Mn-Sn magnetic shape memory alloys exhibit interesting low temperature magnetic properties, including intrinsic superparamagnetism and exchange bias effects, which have previously been rationalized in terms of spin clusters. We show here that spin-echo NMR, involving 55Mn hyperfine fields, permits ferromagnetic and antiferromagnetic nanoregions to be directly identified in these materials and yields estimates of their size distributions. Nuclear relaxation rate measurements, made as a function of temperature, provide information on both the dynamics and on the electronic structure of the nanoregions. The relaxation rates are analyzed using a combination of Redfield and Korringa mechanisms, the Korringa procedure providing information on the density of states at the Fermi level. Results will be presented for a number of these alloys. DMR-1309463.

Probable causes of damage of heat-exchange tubes of low-pressure-exchanges of PND-3 type and repair methods

NASA Astrophysics Data System (ADS)

Trifonov, N. N.; Esin, S. B.; Nikolaenkova, E. K.; Sukhorukov, Yu. G.; Svyatkin, F. A.; Sintsova, T. G.; Modestov, V. S.

2017-08-01

The structures of low-pressure heaters (LPH), which are installed at nuclear power plants with the K-1000-60/1500 type turbine plants are considered. It was revealed that only the PND-3 type low-pressure heaters have the damages of the heat exchange tubes. For a short operation life, the number of the damaged heat-exchange tubes of PND-3 is approximately 50 pcs for Kalinin NPP and 100-150 pcs for Balakovo NPP. The low-pressure heaters were manufactured at AO Ural Plant of Chemical Machine-Building "Uralkhimmash," OAO Taganrog Boiler-Making Works "Krasny Kotelshchik," and Vitkovice Machinery Group, but the damage nature of the heat-exchange tubes is identical for all PND-3. The damages occur in the place of passage of the heat exchange tubes through the first, the second, and the third partitions over the lower tube plate (the first path of the turbine condensate). Hydraulic shocks can be one of the possible causes of the damage of the heat-exchange tubes of PND-3. The analysis of the average thermal and dynamic loads of the tube systems of PND-1-PND-4 revealed that PND-3 by the thermal power are loaded 1.4-1.6 times and by the dynamic effects are loaded 1.8-2.0 times more than the remaining LPHs. Another possible cause of damage can be the cascaded drain of the separate into PND-4 and then through the drainage heat exchange into PND-3. An additional factor can be the structure of the condensate drainage unit. The advanced system of the heating steam flow and pumping scheme of the separate drain using the existing drainage pumps of PND-3 for K-1000-60/1500 turbine plants for Balakovo and Kalinin NPPs were proposed. The considered decisions make it possible to reduce the flow rate of the heating steam condensate from PND-3 into PND-4 and the speed of the heating steam in the tube space of PND-3 and eliminate the occurrence of hydraulic shocks and damages of the heat exchanger tubes.

Materials, Turbomachinery and Heat Exchangers for Supercritical CO2 Systems

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

Anderson, Mark; Nellis, Greg; Corradini, Michael

2012-10-19

The objective of this project is to produce the necessary data to evaluate the performance of the supercritical carbon dioxide cycle. The activities include a study of materials compatibility of various alloys at high temperatures, the heat transfer and pressure drop in compact heat exchanger units, and turbomachinery issues, primarily leakage rates through dynamic seals. This experimental work will serve as a test bed for model development and design calculations, and will help define further tests necessary to develop high-efficiency power conversion cycles for use on a variety of reactor designs, including the sodium fast reactor (SFR) and very high-temperaturemore » gas reactor (VHTR). The research will be broken into three separate tasks. The first task deals with the analysis of materials related to the high-temperature S-CO{sub 2} Brayton cycle. The most taxing materials issues with regard to the cycle are associated with the high temperatures in the reactor side heat exchanger and in the high-temperature turbine. The system could experience pressures as high as 20MPa and temperatures as high as 650°C. The second task deals with optimization of the heat exchangers required by the S-CO{sub 2} cycle; the S-CO{sub 2} flow passages in these heat exchangers are required whether the cycle is coupled with a VHTR or an SFR. At least three heat exchangers will be required: the pre-cooler before compression, the recuperator, and the heat exchanger that interfaces with the reactor coolant. Each of these heat exchangers is unique and must be optimized separately. The most challenging heat exchanger is likely the pre-cooler, as there is only about a 40°C temperature change but it operates close to the CO{sub 2} critical point, therefore inducing substantial changes in properties. The proposed research will focus on this most challenging component. The third task examines seal leakage through various dynamic seal designs under the conditions expected in the S-CO{sub 2} cycle, including supercritical, choked, and two-phase flow conditions.« less

Hydrogen exchange kinetics in a membrane protein determined by sup 15 N NMR spectroscopy: Use of the INEPT (insensitive nucleus enhancement by polarization transfer) experiment to follow individual amides in detergent-solubilized M13 coat protein

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

Henry, G.D.; Sykes, B.D.

The coat protein of the filamentous coliphage M13 is a 50-residue polypeptide which spans the inner membrane of the Escherichia coli host upon infection. Amide hydrogen exchange kinetics have been used to probe the structure and dynamics of M13 coat protein which has been solubilized in sodium dodecyl sulfate (SDS) micelles. In a previous {sup 1}H nuclear magnetic resonance (NMR) study, multiple exponential analysis of the unresolved amide proton envelope revealed the existence of two slow kinetic sets containing a total of about 30 protons. The slower set (15-20 amides) originates from the hydrophobic membrane-spanning region and exchanges at leastmore » 10{sup 5}-fold slower than the unstructured, non-H-bonded model polypeptide poly(DL-alanine). Herein the authors use {sup 15}N NMR spectroscopy of biosynthetically labeled coat protein to follow individual, assigned, slowly exchanging amides in or near the hydrophobic segment. The INEPT (insensitive nucleus enhancement by polarization transfer) experiments can be used to transfer magnetization to the {sup 15}N nucleus from a coupled proton; when {sup 15}N-labeled protonated protein is dissolved in {sup 2}H{sub 2}O, the INEPT signal disappears with time as the amide protons are replaced by solvent deuterons. Amide hydrogen exchange is catalyzed by both H{sup +} and OH{sup {minus}} ions. The time-dependent exchange-out experiment is suitable for slow exchange rates (k{sub ex}). The INEPT experiment was also adapted to measure some of the more rapidly exchanging amides in the coat protein using either saturation transfer from water or exchange effects on the polarization transfer step itself. The results of all of these experiments are consistent with previous models of the coat protein in which a stable segment extends from the hydrophobic membrane-spanning region through to the C-terminus, whereas the N-terminal region is undergoing more extensive dynamic fluctuations.« less

Leaf dynamics and profitability in wild strawberries.

PubMed

Jurik, Thomas W; Chabot, Brian F

1986-05-01

Leaf dynamics and carbon gain were evaluated for two species of wild strawberry, Fragaria virginiana and F. vesca. Five populations on sites representing a gradient of successional regrowth near Ithaca, N.Y., U.S.A., were studied for two or three years each. A computer-based model of plant growth and CO 2 exchange combined field studies of leaf biomass dynamics with previously-determined gas exchange rates to estimate carbon balances of leaves and whole plants in different environments.Leaves were produced throughout the growing season, although there was usually a decline in rate of leaf-production in mid-summer. Leaves produced in late spring had the largest area and longest lifespan (except for overwintering leaves produced in the fall). Specific Leaf Weight (SLW) varied little with time of leaf production, but differed greatly among populations; SLW increased with amount of light received in each habitat. The population in the most open habitat had the least seasonal variation in all leaf characters. F. vesca produced lighter, longer-lived leaves than F. virginiana.Simulations showed that age had the largest effect on leaf carbon gain in high-light environments; water stress and temperature had lesser effects. Leaf carbon gain in lowlight environments was relatively unaffected by age and environmental factors other than light. Leaves in high-light environments had the greatest lifetime profit and the greatest ratio of profit to cost. Increasing lifespan by 1/3 increased profit by 80% in low-light leaves and 50% in high-light leaves. Increasing the number of days during which the leaf had the potential to exhibit high photosynthetic rate in response to high light led to little change in profit of low-light leaves while increasing profit of high-light leaves by 49%.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

HDX Workbench: Software for the Analysis of H/D Exchange MS Data

NASA Astrophysics Data System (ADS)

Pascal, Bruce D.; Willis, Scooter; Lauer, Janelle L.; Landgraf, Rachelle R.; West, Graham M.; Marciano, David; Novick, Scott; Goswami, Devrishi; Chalmers, Michael J.; Griffin, Patrick R.

2012-09-01

Hydrogen/deuterium exchange mass spectrometry (HDX-MS) is an established method for the interrogation of protein conformation and dynamics. While the data analysis challenge of HDX-MS has been addressed by a number of software packages, new computational tools are needed to keep pace with the improved methods and throughput of this technique. To address these needs, we report an integrated desktop program titled HDX Workbench, which facilitates automation, management, visualization, and statistical cross-comparison of large HDX data sets. Using the software, validated data analysis can be achieved at the rate of generation. The application is available at the project home page http://hdx.florida.scripps.edu.

Transient thermal, hydraulic, and mechanical analysis of a counter flow offset strip fin intermediate heat exchanger using an effective porous media approach

NASA Astrophysics Data System (ADS)

Urquiza, Eugenio

This work presents a comprehensive thermal hydraulic analysis of a compact heat exchanger using offset strip fins. The thermal hydraulics analysis in this work is followed by a finite element analysis (FEA) to predict the mechanical stresses experienced by an intermediate heat exchanger (IHX) during steady-state operation and selected flow transients. In particular, the scenario analyzed involves a gas-to-liquid IHX operating between high pressure helium and liquid or molten salt. In order to estimate the stresses in compact heat exchangers a comprehensive thermal and hydraulic analysis is needed. Compact heat exchangers require very small flow channels and fins to achieve high heat transfer rates and thermal effectiveness. However, studying such small features computationally contributes little to the understanding of component level phenomena and requires prohibitive computational effort using computational fluid dynamics (CFD). To address this issue, the analysis developed here uses an effective porous media (EPM) approach; this greatly reduces the computation time and produces results with the appropriate resolution [1]. This EPM fluid dynamics and heat transfer computational code has been named the Compact Heat Exchanger Explicit Thermal and Hydraulics (CHEETAH) code. CHEETAH solves for the two-dimensional steady-state and transient temperature and flow distributions in the IHX including the complicating effects of temperature-dependent fluid thermo-physical properties. Temperature- and pressure-dependent fluid properties are evaluated by CHEETAH and the thermal effectiveness of the IHX is also calculated. Furthermore, the temperature distribution can then be imported into a finite element analysis (FEA) code for mechanical stress analysis using the EPM methods developed earlier by the University of California, Berkeley, for global and local stress analysis [2]. These simulation tools will also allow the heat exchanger design to be improved through an iterative design process which will lead to a design with a reduced pressure drop, increased thermal effectiveness, and improved mechanical performance as it relates to creep deformation and transient thermal stresses.

Experimental evidence for importance of Hund's exchange interaction for incoherence of charge carriers in iron-based superconductors

NASA Astrophysics Data System (ADS)

Fink, J.; Rienks, E. D. L.; Thirupathaiah, S.; Nayak, J.; van Roekeghem, A.; Biermann, S.; Wolf, T.; Adelmann, P.; Jeevan, H. S.; Gegenwart, P.; Wurmehl, S.; Felser, C.; Büchner, B.

2017-04-01

Angle-resolved photoemission spectroscopy is used to study the scattering rates of charge carriers from the hole pockets near Γ in the iron-based high-Tc hole-doped superconductors KxBa1 -xFe2As2 , x =0.4 , and KxEu1 -xFe2As2 , x =0.55 , and the electron-doped compound Ba (Fe1-xCox) 2As2 , x =0.075 . The scattering rate for any given band is found to depend linearly on the energy, indicating a non-Fermi-liquid regime. The scattering rates in the hole-doped compound are considerably higher than those in the electron-doped compounds. In the hole-doped systems the scattering rate of the charge carriers of the inner hole pocket is about three times higher than the binding energy, indicating that the spectral weight is heavily incoherent. The strength of the scattering rates and the difference between electron- and hole-doped compounds signals the importance of Hund's exchange coupling for correlation effects in these iron-based high-Tc superconductors. The experimental results are in qualitative agreement with theoretical calculations in the framework of combined density functional dynamical mean-field theory.

Dynamic NMR of Intramolecular Exchange Processes in EDTA Complexes of Sc[superscript 3+], Y[superscript 3+], and La[superscript 3+

ERIC Educational Resources Information Center

Ba, Yong; Han, Steven; Ni, Lily; Su, Tony; Garcia, Andres

2006-01-01

Dynamic NMR makes use of the effect of chemical exchanges on NMR spectra to study kinetics and thermodynamics. An advanced physical chemistry lab experiment was developed to study the intramolecular exchange processes of EDTA (the disodium salt of ethylenediaminetetraacetic acid) metal complexes. EDTA is an important chelating agent, used in…

Examining the reaction of monetary policy to exchange rate changes: A nonlinear ARDL approach

NASA Astrophysics Data System (ADS)

Manogaran, Lavaneesvari; Sek, Siok Kun

2017-04-01

Previous studies showed the exchange rate changes can have significant impacts on macroeconomic performance. Over fluctuation of exchange rate may lead to economic instability. Hence, monetary policy rule tends to react to exchange rate changes. Especially, in emerging economies where the policy-maker tends to limit the exchange rate movement through interventions. In this study, we seek to investigate how the monetary policy rule reacts to exchange rate changes. The nonlinear autoregressive distributed lag (NARDL) model is applied to capture the asymmetric effect of exchange rate changes on monetary policy reaction function (interest rate). We focus the study in ASEAN5 countries (Indonesia, Malaysia, Philippines, Thailand and Singapore). The results indicated the existence of asymmetric effect of exchange rates changes on the monetary reaction function for all ASEAN5 countries in the long-run. Where, in majority of the cases the monetary policy is reacting to the appreciation and depreciation of exchange rate by raising the policy rate. This affirms the intervention of policymakers with the `fear of floating' behavior.

Ultrafast Photoinduced Multimode Antiferromagnetic Spin Dynamics in Exchange-Coupled Fe/RFeO3 (R = Er or Dy) Heterostructures.

PubMed

Tang, Jin; Ke, Yajiao; He, Wei; Zhang, Xiangqun; Zhang, Wei; Li, Na; Zhang, Yongsheng; Li, Yan; Cheng, Zhaohua

2018-05-25

Antiferromagnetic spin dynamics is important for both fundamental and applied antiferromagnetic spintronic devices; however, it is rarely explored by external fields because of the strong exchange interaction in antiferromagnetic materials. Here, the photoinduced excitation of ultrafast antiferromagnetic spin dynamics is achieved by capping antiferromagnetic RFeO 3 (R = Er or Dy) with an exchange-coupled ferromagnetic Fe film. Compared with antiferromagnetic spin dynamics of bare RFeO 3 orthoferrite single crystals, which can be triggered effectively by ultrafast laser heating just below the phase transition temperature, the ultrafast photoinduced multimode antiferromagnetic spin dynamic modes, for exchange-coupled Fe/RFeO 3 heterostructures, including quasiferromagnetic resonance, impurity, coherent phonon, and quasiantiferromagnetic modes, are observed in a temperature range of 10-300 K. These experimental results not only offer an effective means to trigger ultrafast antiferromagnetic spin dynamics of rare-earth orthoferrites, but also shed light on the ultrafast manipulation of antiferromagnetic magnetization in Fe/RFeO 3 heterostructures. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamic control of nutrient-removal from industrial wastewater in a sequencing batch reactor, using common and low-cost online sensors.

PubMed

Dries, Jan

2016-01-01

On-line control of the biological treatment process is an innovative tool to cope with variable concentrations of chemical oxygen demand and nutrients in industrial wastewater. In the present study we implemented a simple dynamic control strategy for nutrient-removal in a sequencing batch reactor (SBR) treating variable tank truck cleaning wastewater. The control system was based on derived signals from two low-cost and robust sensors that are very common in activated sludge plants, i.e. oxidation reduction potential (ORP) and dissolved oxygen. The amount of wastewater fed during anoxic filling phases, and the number of filling phases in the SBR cycle, were determined by the appearance of the 'nitrate knee' in the profile of the ORP. The phase length of the subsequent aerobic phases was controlled by the oxygen uptake rate measured online in the reactor. As a result, the sludge loading rate (F/M ratio), the volume exchange rate and the SBR cycle length adapted dynamically to the activity of the activated sludge and the actual characteristics of the wastewater, without affecting the final effluent quality.

Dynamics of Water in Gemini Surfactant-Based Lyotropic Liquid Crystals

DOE PAGES

McDaniel, Jesse G.; Mantha, Sriteja; Yethiraj, Arun

2016-09-26

The dynamics of water confined to nanometer-sized domains is important in a variety of applications ranging from proton exchange membranes to crowding effects in biophysics. In this work we study the dynamics of water in gemini surfactant-based lyotropic liquid crystals (LLCs) using molecular dynamics simulations. These systems have well characterized morphologies, e.g., hexagonal, gyroid, and lamellar, and the surfaces of the confining regions can be controlled by modifying the headgroup of the surfactants. This allows one to study the effect of topology, functionalization, and interfacial curvature on the dynamics of confined water. Through analysis of the translational diffusion and rotationalmore » relaxation we conclude that the hydration level and resulting confinement lengthscale is the predominate determiner of the rates of water dynamics, and other effects, namely surface functionality and curvature, are largely secondary. In conclusion, this novel analysis of the water dynamics in these LLC systems provides an important comparison for previous studies of water dynamics in lipid bilayers and reverse micelles.« less

A permutationally invariant full-dimensional ab initio potential energy surface for the abstraction and exchange channels of the H + CH{sub 4} system

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

Li, Jun, E-mail: jli15@cqu.edu.cn, E-mail: zhangdh@dicp.ac.cn; Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131; Chen, Jun

2015-05-28

We report a permutationally invariant global potential energy surface (PES) for the H + CH{sub 4} system based on ∼63 000 data points calculated at a high ab initio level (UCCSD(T)-F12a/AVTZ) using the recently proposed permutation invariant polynomial-neural network method. The small fitting error (5.1 meV) indicates a faithful representation of the ab initio points over a large configuration space. The rate coefficients calculated on the PES using tunneling corrected transition-state theory and quasi-classical trajectory are found to agree well with the available experimental and previous quantum dynamical results. The calculated total reaction probabilities (J{sub tot} = 0) including themore » abstraction and exchange channels using the new potential by a reduced dimensional quantum dynamic method are essentially the same as those on the Xu-Chen-Zhang PES [Chin. J. Chem. Phys. 27, 373 (2014)].« less

Seasonal and diurnal gas exchange differences in ozone-sensitive common milkweed (Asclepias syriaca L.) in relation to ozone uptake.

PubMed

Bergweiler, Chris; Manning, William J; Chevone, Boris I

2008-03-01

Stomatal conductance and net photosynthesis of common milkweed (Asclepias syriaca L.) plants in two different soil moisture regimes were directly quantified and subsequently modeled over an entire growing season. Direct measurements captured the dynamic response of stomatal conductance to changing environmental conditions throughout the day, as well as declining gas exchange and carbon assimilation throughout the growth period beyond an early summer maximum. This phenomenon was observed in plants grown both with and without supplemental soil moisture, the latter of which should theoretically mitigate against harmful physiological effects caused by exposure to ozone. Seasonally declining rates of stomatal conductance were found to be substantial and incorporated into models, making them less susceptible to the overestimations of effective exposure that are an inherent source of error in ozone exposure indices. The species-specific evidence presented here supports the integration of dynamic physiological processes into flux-based modeling approaches for the prediction of ozone injury in vegetation.

Exchange rate rebounds after foreign exchange market interventions

NASA Astrophysics Data System (ADS)

Hoshikawa, Takeshi

2017-03-01

This study examined the rebounds in the exchange rate after foreign exchange intervention. When intervention is strongly effective, the exchange rate rebounds at next day. The effect of intervention is reduced slightly by the rebound after the intervention. The exchange rate might have been 67.12-77.47 yen to a US dollar without yen-selling/dollar-purchasing intervention of 74,691,100 million yen implemented by the Japanese government since 1991, in comparison to the actual exchange rate was 103.19 yen to the US dollar at the end of March 2014.

Dynamic adsorption of CO2/N2 on cation-exchanged chabazite SSZ-13: A breakthrough analysis

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

Bower, Jamey K.; Barpaga, Dushyant; Prodinger, Sebastian

2018-04-17

Alkali exchanged SSZ-13 adsorbents were investigated for their applicability in separating N2 from CO2 in flue gas streams using a dynamic breakthrough method. In contrast to IAST calculations based on equilibrium isotherms, K+ exchanged SSZ-13 was found to yield the best N2 productivity under dynamic conditions where diffusion properties play a significant role. This was attributed to the selective, partial blockage of access to the CHA cavities enhancing the separation potential in a 15/85 CO2/N2 binary gas mixture.

Dynamic Adsorption of CO 2 /N 2 on Cation-Exchanged Chabazite SSZ-13: A Breakthrough Analysis

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

Bower, Jamey K.; Barpaga, Dushyant; Prodinger, Sebastian

2018-03-30

Alkali exchanged SSZ-13 adsorbents were investigated for their applicability in separating N2 from CO 2 in flue gas streams using a dynamic breakthrough method. In contrast to IAST calculations based on equilibrium isotherms, K+ exchanged SSZ-13 was found to yield the best N2 productivity under dynamic conditions where diffusion properties play a significant role. This was attributed to the selective, partial blockage of access to the CHA cavities enhancing the separation potential in a 15/85 CO2/N2 binary gas mixture.

NMR studies of the backbone flexibility and structure of human growth hormone: a comparison of high and low pH conformations.

PubMed

Kasimova, Marina R; Kristensen, Søren M; Howe, Peter W A; Christensen, Thorkild; Matthiesen, Finn; Petersen, Jørgen; Sørensen, Hans H; Led, Jens J

2002-05-03

(15)N NMR relaxation parameters and amide (1)H/(2)H-exchange rates have been used to characterize the structural flexibility of human growth hormone (rhGH) at neutral and acidic pH. Our results show that the rigidity of the molecule is strongly affected by the solution conditions. At pH 7.0 the backbone dynamics parameters of rhGH are uniform along the polypeptide chain and their values are similar to those of other folded proteins. In contrast, at pH 2.7 the overall backbone flexibility increases substantially compared to neutral pH and the average order parameter approaches the lower limit expected for a folded protein. However, a significant variation of the backbone dynamics through the molecule indicates that under acidic conditions the mobility of the residues becomes more dependent on their location within the secondary structure units. In particular, the order parameters of certain loop regions decrease dramatically and become comparable to those found in unfolded proteins. Furthermore, the HN-exchange rates at low pH reveal that the residues most protected from exchange are clustered at one end of the helical bundle, forming a stable nucleus. We suggest that this nucleus maintains the overall fold of the protein under destabilizing conditions. We therefore conclude that the acid state of rhGH consists of a structurally conserved, but dynamically more flexible helical core surrounded by an aura of highly mobile, unstructured loops. However, in spite of its prominent flexibility the acid state of rhGH cannot be considered a "molten globule" state because of its high stability. It appears from our work that under certain conditions, a protein can tolerate a considerable increase in flexibility of its backbone, along with an increased penetration of water into its core, while still maintaining a stable folded conformation.

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

PubMed

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

2011-09-14

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

Knowledge exchange and integrated services: experiences from an integrated community intellectual (learning) disability service for adults.

PubMed

Farrington, C; Clare, I C H; Holland, A J; Barrett, M; Oborn, E

2015-03-01

This paper examines knowledge exchange dynamics in a specialist integrated intellectual (learning) disability service, comprising specialist healthcare provision with social care commissioning and management, and considers their significance in terms of integrated service delivery. A qualitative study focusing on knowledge exchange and integrated services. Semi-structured interviews (n = 25) were conducted with members of an integrated intellectual disability service in England regarding their perceptions of knowledge exchange within the service and the way in which knowledge exchange impinges on the operation of the integrated service. Exchange of 'explicit' (codifiable) knowledge between health and care management components of the service is problematic because of a lack of integrated clinical governance and related factors such as IT and care record systems and office arrangements. Team meetings and workplace interactions allowed for informal exchange of explicit and 'tacit' (non-codifiable) knowledge, but presented challenges in terms of knowledge exchange completeness and sustainability. Knowledge exchange processes play an important role in the functioning of integrated services incorporating health and care management components. Managers need to ensure that knowledge exchange processes facilitate both explicit and tacit knowledge exchange and do not rely excessively on informal, 'ad hoc' interactions. Research on integrated services should take account of micro-scale knowledge exchange dynamics and relationships between social dynamics and physical factors. © 2014 MENCAP and International Association of the Scientific Study of Intellectual and Developmental Disabilities and John Wiley & Sons Ltd.

Efficient Conformational Sampling in Explicit Solvent Using a Hybrid Replica Exchange Molecular Dynamics Method

DTIC Science & Technology

2011-12-01

REMD while reproducing the energy landscape of explicit solvent simulations . ’ INTRODUCTION Molecular dynamics (MD) simulations of proteins can pro...Mongan, J.; McCammon, J. A. Accelerated molecular dynamics : a promising and efficient simulation method for biomolecules. J. Chem. Phys. 2004, 120 (24...Chemical Theory and Computation ARTICLE (8) Abraham,M. J.; Gready, J. E. Ensuringmixing efficiency of replica- exchange molecular dynamics simulations . J

Theoretical rate constants of super-exchange hole transfer and thermally induced hopping in DNA.

PubMed

Shimazaki, Tomomi; Asai, Yoshihiro; Yamashita, Koichi

2005-01-27

Recently, the electronic properties of DNA have been extensively studied, because its conductivity is important not only to the study of fundamental biological problems, but also in the development of molecular-sized electronics and biosensors. We have studied theoretically the reorganization energies, the activation energies, the electronic coupling matrix elements, and the rate constants of hole transfer in B-form double-helix DNA in water. To accommodate the effects of DNA nuclear motions, a subset of reaction coordinates for hole transfer was extracted from classical molecular dynamics (MD) trajectories of DNA in water and then used for ab initio quantum chemical calculations of electron coupling constants based on the generalized Mulliken-Hush model. A molecular mechanics (MM) method was used to determine the nuclear Franck-Condon factor. The rate constants for two types of mechanisms of hole transfer-the thermally induced hopping (TIH) and the super-exchange mechanisms-were determined based on Marcus theory. We found that the calculated matrix elements are strongly dependent on the conformations of the nucleobase pairs of hole-transferable DNA and extend over a wide range of values for the "rise" base-step parameter but cluster around a particular value for the "twist" parameter. The calculated activation energies are in good agreement with experimental results. Whereas the rate constant for the TIH mechanism is not dependent on the number of A-T nucleobase pairs that act as a bridge, the rate constant for the super-exchange process rapidly decreases when the length of the bridge increases. These characteristic trends in the calculated rate constants effectively reproduce those in the experimental data of Giese et al. [Nature 2001, 412, 318]. The calculated rate constants were also compared with the experimental results of Lewis et al. [Nature 2000, 406, 51].

[Soil respiration dynamics and its controlling factors of typical vegetation communities on meadow steppes in the western Songnen Plain].

PubMed

Wang, Ming; Liu, Xing-Tu; Li, Xiu-Jun; Zhang, Ji-Tao; Wang, Guo-Dong; Lu, Xin-Rui; Li, Xiao-Yu

2014-01-01

In order to accurately explore the soil respiration dynamics and its controlling factors of typical vegetation types in the western Songnen Plain, soil respiration rates of Chloris virgata, Puccinellia distans, Phragmites australis and Leymus chinensis communities were measured. The results showed that the diurnal curves of soil respiration rates of the four vegetation communities had simple peak values, which appeared at 11:00-15:00, and the valley values occurred at 21:00-1:00 or 3:00-5:00. The seasonal dynamic patterns of their soil respiration rates were similar, with the maximum (3.21-4.84 micromol CO2 x m(-2) x s(-1)) occurring in July and August and the minimum (0.46-1.51 micromol CO2 x m(-2) x s(-1)) in October. The soil respiration rates of the four vegetation communities had significant exponential correlations with ambient air temperature and soil temperature. Soil moisture, however, only played an important role in affecting the soil respiration rate of C. virgata community while air humidity near the soil surface was significantly correlated with the soil respiration rates of P. australis and L. chinensis communities. The soil salt contents seriously constrained the CO2 dioxide emission, and the soil pH, electrical conductivity (EC), exchangeable sodium percentage (ESP) could explain 87%-91% spatial variations of the soil respiration rate.

Effect of Water Chemistry and Hydrodynamics on Nitrogen Transformation Activity and Microbial Community Functional Potential in Hyporheic Zone Sediment Columns

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

Liu, Yuanyuan; Liu, Chongxuan; Nelson, William C.

Nitrogen (N) transformation in hyporheic zone (HZ) is an important component in N-cycling in ecosystems. A column study was conducted to investigate N transformation in a HZ sediment with a focus on how characteristic HZ properties including water chemistry, fluid residence time, and dynamic groundwater and surface water exchange affect on N transformation. Metagenomic and quantitative polymerase chain reaction (qPCR) analyses were performed to evaluate the dynamic changes in microbial community structure and its function in response to N transformation. The results indicated that N transformation in the HZ sediment was collectively controlled by microbial community functions including: denitrification, dissimilatorymore » nitrate reduction to ammonium (DNRA), nitrification, and anaerobic ammonium oxidation (anammox). However, the spatial distribution of the microbial community functions and associated biogeochemical reaction rates and products changed quickly in response to experimental perturbation, and was influenced by various factors including water chemistry (dissolved O2 and N species), desorption of sediment associated organic carbon, ion exchange reactions of NH4+, and fluid residence time. The results of this study implied that the microbial community in the HZ would exhibit strong function zonation along N and O gradients, which in turn would control the rates and products of N transformation.« less

BARTER: Behavior Profile Exchange for Behavior-Based Admission and Access Control in MANETs

NASA Astrophysics Data System (ADS)

Frias-Martinez, Vanessa; Stolfo, Salvatore J.; Keromytis, Angelos D.

Mobile Ad-hoc Networks (MANETs) are very dynamic networks with devices continuously entering and leaving the group. The highly dynamic nature of MANETs renders the manual creation and update of policies associated with the initial incorporation of devices to the MANET (admission control) as well as with anomaly detection during communications among members (access control) a very difficult task. In this paper, we present BARTER, a mechanism that automatically creates and updates admission and access control policies for MANETs based on behavior profiles. BARTER is an adaptation for fully distributed environments of our previously introduced BB-NAC mechanism for NAC technologies. Rather than relying on a centralized NAC enforcer, MANET members initially exchange their behavior profiles and compute individual local definitions of normal network behavior. During admission or access control, each member issues an individual decision based on its definition of normalcy. Individual decisions are then aggregated via a threshold cryptographic infrastructure that requires an agreement among a fixed amount of MANET members to change the status of the network. We present experimental results using content and volumetric behavior profiles computed from the ENRON dataset. In particular, we show that the mechanism achieves true rejection rates of 95% with false rejection rates of 9%.

Dynamics of spontaneous flipping of a mismatched base in DNA duplex.

PubMed

Yin, Yandong; Yang, Lijiang; Zheng, Guanqun; Gu, Chan; Yi, Chengqi; He, Chuan; Gao, Yi Qin; Zhao, Xin Sheng

2014-06-03

DNA base flipping is a fundamental theme in DNA biophysics. The dynamics for a B-DNA base to spontaneously flip out of the double helix has significant implications in various DNA-protein interactions but are still poorly understood. The spontaneous base-flipping rate obtained previously via the imino proton exchange assay is most likely the rate of base wobbling instead of flipping. Using the diffusion-decelerated fluorescence correlation spectroscopy together with molecular dynamics simulations, we show that a base of a single mismatched base pair (T-G, T-T, or T-C) in a double-stranded DNA can spontaneously flip out of the DNA duplex. The extrahelical lifetimes are on the order of 10 ms, whereas the intrahelical lifetimes range from 0.3 to 20 s depending on the stability of the base pairs. These findings provide detailed understanding on the dynamics of DNA base flipping and lay down foundation to fully understand how exactly the repair proteins search and locate the target mismatched base among a vast excess of matched DNA bases.

Respiratory dynamics of discontinuous gas exchange in the tracheal system of the desert locust, Schistocerca gregaria.

PubMed

Groenewald, Berlizé; Hetz, Stefan K; Chown, Steven L; Terblanche, John S

2012-07-01

Gas exchange dynamics in insects is of fundamental importance to understanding evolved variation in breathing patterns, such as discontinuous gas exchange cycles (DGCs). Most insects do not rely solely on diffusion for the exchange of respiratory gases but may also make use of respiratory movements (active ventilation) to supplement gas exchange at rest. However, their temporal dynamics have not been widely investigated. Here, intratracheal pressure, V(CO2) and body movements of the desert locust Schistocerca gregaria were measured simultaneously during the DGC and revealed several important aspects of gas exchange dynamics. First, S. gregaria employs two different ventilatory strategies, one involving dorso-ventral contractions and the other longitudinal telescoping movements. Second, although a true spiracular closed (C)-phase of the DGC could be identified by means of subatmospheric intratracheal pressure recordings, some CO(2) continued to be released. Third, strong pumping actions do not necessarily lead to CO(2) release and could be used to ensure mixing of gases in the closed tracheal system, or enhance water vapour reabsorption into the haemolymph from fluid-filled tracheole tips by increasing the hydrostatic pressure or forcing fluid into the haemocoel. Finally, this work showed that the C-phase of the DGC can occur at any pressure. These results provide further insights into the mechanistic basis of insect gas exchange.

Carbon partitioning patterns of mycorrhizal versus non-mycorrhizal plants: real-time dynamic measurements using 11 CO2.

PubMed

Wang, G M; Coleman, D C; Freckman, D W; Dyer, M I; McNAUGHTON, S J; Agra, M A; Goeschl, J D

1989-08-01

Gas exchange and carbon allocation patterns were studied in two populations of Panicum coloratum, an Africa C-4 grass. The plants were grown in split-root pots, containing partially sterilized soil, with one side either inoculated (I) or not inoculated (NI) with a vesicular arbuscular (VA) mycorrhizal Fungus, Gigaspora margarita. Net carbon exchange rates (CER) and stomatal conductances were measured with conventional gas exchange apparatus, and carbon assimilation, translocation, and allocation were measured using photosynthetically-fixed 11 CO 2 . Mycorrhizal infection on one half of the split-root system caused a 20%, increase in CER. The effect on CER was less in tillers on the opposite side of the plants from the infected half of the roots. The rate at which photosynthates were stored in the leaves was 45% higher. Sink activity (concentration of labelled photosynthates in stem phloem tissue) more than doubled in 1 versus NI plants. CER and stomatal conductances, along with most of the carbon allocation patterns, were nearly identical between the NI (control) high grazing and low grazing ecotypes. However, VA mycorrhizal fungi caused a greater storage of photosynthates in the low grazing ecotype.

Capillary trap column with strong cation-exchange monolith for automated shotgun proteome analysis.

PubMed

Wang, Fangjun; Dong, Jing; Jiang, Xiaogang; Ye, Mingliang; Zou, Hanfa

2007-09-01

A 150 microm internal diameter capillary monolithic column with a strong cation-exchange stationary phase was prepared by direct in situ polymerization of ethylene glycol methacrylate phosphate and bisacrylamide in a trinary porogenic solvent consisting dimethylsulfoxide, dodecanol, and N,N'-dimethylformamide. This phosphate monolithic column exhibits higher dynamic binding capacity, faster kinetic adsorption of peptides, and more than 10 times higher permeability than the column packed with commercially available strong cation-exchange particles. It was applied as a trap column in a nanoflow liquid chromatography-tandem mass spectrometry system for automated sample injection and online multidimensional separation. It was observed that the sample could be loaded at a flow rate as high as 40 microL/min with a back pressure of approximately 1300 psi and without compromising the separation efficiency. Because of its good orthogonality to the reversed phase separation mechanism, the phosphate monolithic trap column was coupled with a reversed-phase column for online multidimensional separation of 19 microg of the tryptic digest of yeast proteins. A total of 1522 distinct proteins were identified from 5608 unique peptides (total of 54,780 peptides) at the false positive rate only 0.46%.

Molecular Dynamics Underlie the Nature of MRI Signals: The NMR Shutter-Speed

NASA Astrophysics Data System (ADS)

Springer, Charles S., Jr.

2007-03-01

Motions of the spin-bearing molecules can have profound effects on the very nature (the exponentiality) of the macroscopic NMR signal. Quantitative mechanistic protocols often involve varying the equilibrium molecular kinetics (usually by temperature change) relative to the ``NMR time-scale'' (SS-1), usually ill-defined as the absolute difference of resonance frequencies [|δφ|] in sites between which spins are exchanged. This holds true for the equilibrium water molecule exchange between tissue compartments and distinct populations. However, in vivo studies must [by regulation] be isothermal, and the tissue ^1H2O MRI signals remain essentially isochronous [δφ = 0]. In NMR, an equilibrium process is manifest in the context of its ``exchange condition.'' It only ``appears'' to be fast or slow by comparison of its actual rate constant with its system ``shutter-speed'' (SS). [A nonzero δφ is the first, but not only, SS: its dimension is reciprocal time.] The process kinetics can be measured only if its NMR condition is varied at least partway between the fast- and slow exchange limits. In an isothermal study with no catalyst, this can be accomplished only by varying the pertinent SS. An MRI contrast reagent (CR) increases the laboratory frame ^1H2O relaxation rate constant, Ri [≡ (Ti)-1; i = 1,2]. For an isochronous exchange process, the SS is the intrinsic |δRi| for the sites. In quantitative dynamic-contrast-enhanced (DCE) studies, analytical pharmacokinetic modeling is accomplished on region-of-interest (ROI) or pixel by pixel ^1H2O signal time-courses following bolus CR injections. Accounting for the equilibrium transendothelial and transcytolemmal water interchange processes (a three-site exchange situation) is crucial for modeling accuracy: the relevant SS values vary during the CR bolus passage. This is so for DCE studies of cancer, multiple sclerosis, and myocardial blood flow variation. It is necessary for the successful discrimination of malignant and benign breast and prostate lesions. One can expect a SS for almost any NMR experiment. This includes diffusion weighted and rotating-frame longitudinal relaxation of in vivo ^1H2O signals. In these latter cases, the pertinent SS can be manipulated solely by adjustment of pulse sequence parameters, leading to completely non-invasive protocols.

Role of Detergents in Conformational Exchange of a G Protein-coupled Receptor*

PubMed Central

Chung, Ka Young; Kim, Tae Hun; Manglik, Aashish; Alvares, Rohan; Kobilka, Brian K.; Prosser, R. Scott

2012-01-01

The G protein-coupled β2-adrenoreceptor (β2AR) signals through the heterotrimeric G proteins Gs and Gi and β-arrestin. As such, the energy landscape of β2AR-excited state conformers is expected to be complex. Upon tagging Cys-265 of β2AR with a trifluoromethyl probe, 19F NMR was used to assess conformations and possible equilibria between states. Here, we report key differences in β2AR conformational dynamics associated with the detergents used to stabilize the receptor. In dodecyl maltoside (DDM) micelles, the spectra are well represented by a single Lorentzian line that shifts progressively downfield with activation by appropriate ligand. The results are consistent with interconversion between two or more states on a time scale faster than the greatest difference in ligand-dependent chemical shift (i.e. >100 Hz). Given that high detergent off-rates of DDM monomers may facilitate conformational exchange between functional states of β2AR, we utilized the recently developed maltose-neopentyl glycol (MNG-3) diacyl detergent. In MNG-3 micelles, spectra indicated at least three distinct states, the relative populations of which depended on ligand, whereas no ligand-dependent shifts were observed, consistent with the slow exchange limit. Thus, detergent has a profound effect on the equilibrium kinetics between functional states. MNG-3, which has a critical micelle concentration in the nanomolar regime, exhibits an off-rate that is 4 orders of magnitude lower than that of DDM. High detergent off-rates are more likely to facilitate conformational exchange between distinct functional states associated with the G protein-coupled receptor. PMID:22893704

Role of detergents in conformational exchange of a G protein-coupled receptor.

PubMed

Chung, Ka Young; Kim, Tae Hun; Manglik, Aashish; Alvares, Rohan; Kobilka, Brian K; Prosser, R Scott

2012-10-19

The G protein-coupled β(2)-adrenoreceptor (β(2)AR) signals through the heterotrimeric G proteins G(s) and G(i) and β-arrestin. As such, the energy landscape of β(2)AR-excited state conformers is expected to be complex. Upon tagging Cys-265 of β(2)AR with a trifluoromethyl probe, (19)F NMR was used to assess conformations and possible equilibria between states. Here, we report key differences in β(2)AR conformational dynamics associated with the detergents used to stabilize the receptor. In dodecyl maltoside (DDM) micelles, the spectra are well represented by a single Lorentzian line that shifts progressively downfield with activation by appropriate ligand. The results are consistent with interconversion between two or more states on a time scale faster than the greatest difference in ligand-dependent chemical shift (i.e. >100 Hz). Given that high detergent off-rates of DDM monomers may facilitate conformational exchange between functional states of β(2)AR, we utilized the recently developed maltose-neopentyl glycol (MNG-3) diacyl detergent. In MNG-3 micelles, spectra indicated at least three distinct states, the relative populations of which depended on ligand, whereas no ligand-dependent shifts were observed, consistent with the slow exchange limit. Thus, detergent has a profound effect on the equilibrium kinetics between functional states. MNG-3, which has a critical micelle concentration in the nanomolar regime, exhibits an off-rate that is 4 orders of magnitude lower than that of DDM. High detergent off-rates are more likely to facilitate conformational exchange between distinct functional states associated with the G protein-coupled receptor.

Natural radium and radon tracers to quantify water exchange and movement in reservoirs

USGS Publications Warehouse

Smith, Christopher G.; Baskaran, Mark

2011-01-01

Radon and radium isotopes are routinely used to quantify exchange rates between different hydrologic reservoirs. Since their recognition as oceanic tracers in the 1960s, both radon and radium have been used to examine processes such as air-sea exchange, deep oceanic mixing, benthic inputs, and many others. Recently, the application of radon-222 and the radium-quartet (223,224,226,228Ra) as coastal tracers has seen a revelation with the growing interest in coastal groundwater dynamics. The enrichment of these isotopes in benthic fluids including groundwater makes both radium and radon ideal tracers of coastal benthic processes (e.g. submarine groundwater discharge). In this chapter we review traditional and recent advances in the application of radon and radium isotopes to understand mixing and exchange between various hydrologic reservoirs, specifically: (1) atmosphere and ocean, (2) deep and shallow oceanic water masses, (3) coastal groundwater/benthic pore waters and surface ocean, and (4) aquifer-lakes. While the isotopes themselves and their distribution in the environment provide qualitative information about the exchange processes, it is mixing/exchange and transport models for these isotopes that provide specific quantitative information about these processes. Brief introductions of these models and mixing parameters are provided for both historical and more recent studies.

Laboratory-Scale Column Testing Using IONSIV IE-911 for Removing Cesium from Acidic Tank Waste Simulant. 1: Cesium Exchange Capacity of a 15-cm3 Column and Dynamic Stability of the Exchange Media

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

T.J. Tranter; R.D. Tillotson; T.A. Todd

2005-04-01

Bench-scale column tests were performed using a commercial form of crystalline silicotitanate (CST) for removing radio-cesium from a surrogate acidic tank solution representative of liquid waste stored at the Idaho National Engineering and Environmental Laboratory (INEEL). An engineered form of CST ion exchanger, known as IONSIVtm IE-911 (UOP, Mt Laurel, NJ, USA), was tested in 15 cm3 columns at a flow rate of 5 bed volumes per hour. These experiments showed the ion exchange material to have reasonable selectivity and capacity for removing cesium from the complex chemical matrix of the solution. However, previous testing indicated that partial neutralization ofmore » the feed stream was necessary to increase the stability of the ion exchange media. Thus, in these studies, CST degradation was determined as a function of throughput in order to better assess the stability characteristics of the exchanger for potential future waste treatment applications. Results of these tests indicate that the degradation of the CST reaches a maximum very soon after the acidic feed is introduced to the column and then rapidly declines. Total dissolution of bed material did not exceed 3% under the experimental regime used.« less

Variations in atmospheric CO2 growth rates coupled with tropical temperature

PubMed Central

Wang, Weile; Ciais, Philippe; Nemani, Ramakrishna R.; Canadell, Josep G.; Piao, Shilong; Sitch, Stephen; White, Michael A.; Hashimoto, Hirofumi; Milesi, Cristina; Myneni, Ranga B.

2013-01-01

Previous studies have highlighted the occurrence and intensity of El Niño–Southern Oscillation as important drivers of the interannual variability of the atmospheric CO2 growth rate, but the underlying biogeophysical mechanisms governing such connections remain unclear. Here we show a strong and persistent coupling (r2 ≈ 0.50) between interannual variations of the CO2 growth rate and tropical land–surface air temperature during 1959 to 2011, with a 1 °C tropical temperature anomaly leading to a 3.5 ± 0.6 Petagrams of carbon per year (PgC/y) CO2 growth-rate anomaly on average. Analysis of simulation results from Dynamic Global Vegetation Models suggests that this temperature–CO2 coupling is contributed mainly by the additive responses of heterotrophic respiration (Rh) and net primary production (NPP) to temperature variations in tropical ecosystems. However, we find a weaker and less consistent (r2 ≈ 0.25) interannual coupling between CO2 growth rate and tropical land precipitation than diagnosed from the Dynamic Global Vegetation Models, likely resulting from the subtractive responses of tropical Rh and NPP to precipitation anomalies that partly offset each other in the net ecosystem exchange (i.e., net ecosystem exchange ≈ Rh − NPP). Variations in other climate variables (e.g., large-scale cloudiness) and natural disturbances (e.g., volcanic eruptions) may induce transient reductions in the temperature–CO2 coupling, but the relationship is robust during the past 50 y and shows full recovery within a few years after any such major variability event. Therefore, it provides an important diagnostic tool for improved understanding of the contemporary and future global carbon cycle. PMID:23884654

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

NASA Astrophysics Data System (ADS)

Shinzawa, Hideyuki; Mizukado, Junji

2018-05-01

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

Computational methods and challenges in hydrogen/deuterium exchange mass spectrometry.

PubMed

Claesen, Jürgen; Burzykowski, Tomasz

2017-09-01

Hydrogen/Deuterium exchange (HDX) has been applied, since the 1930s, as an analytical tool to study the structure and dynamics of (small) biomolecules. The popularity of using HDX to study proteins increased drastically in the last two decades due to the successful combination with mass spectrometry (MS). Together with this growth in popularity, several technological advances have been made, such as improved quenching and fragmentation. As a consequence of these experimental improvements and the increased use of protein-HDXMS, large amounts of complex data are generated, which require appropriate analysis. Computational analysis of HDXMS requires several steps. A typical workflow for proteins consists of identification of (non-)deuterated peptides or fragments of the protein under study (local analysis), or identification of the deuterated protein as a whole (global analysis); determination of the deuteration level; estimation of the protection extent or exchange rates of the labile backbone amide hydrogen atoms; and a statistically sound interpretation of the estimated protection extent or exchange rates. Several algorithms, specifically designed for HDX analysis, have been proposed. They range from procedures that focus on one specific step in the analysis of HDX data to complete HDX workflow analysis tools. In this review, we provide an overview of the computational methods and discuss outstanding challenges. © 2016 Wiley Periodicals, Inc. Mass Spec Rev 36:649-667, 2017. © 2016 Wiley Periodicals, Inc.

Impact of transient stream flow on water exchange and reactions in the hyporheic zone of an in-stream gravel bar

NASA Astrophysics Data System (ADS)

Trauth, Nico; Schmidt, Christian; Fleckenstein, Jan H.

2015-04-01

Groundwater-surface water exchange is an important process that can facilitate the degradation of critical substances like nitrogen-species and contaminants, supporting a healthy status of the aquatic ecosystem. In our study, we simulate water exchange, solute transport and reactions within a natural in-stream gravel bar using a coupled surface and subsurface numerical model. Stream water flow is simulated by computational fluid dynamics software that provides hydraulic head distributions at the streambed, which are used as an upper boundary condition for a groundwater model. In the groundwater model water exchange, solute transport, aerobic respiration and denitrification in the subsurface are simulated. Ambient groundwater flow is introduced by lateral upstream and downstream hydraulic head boundaries that generate neutral, losing or gaining stream conditions. Stream water transports dissolved oxygen, organic carbon (as the dominant electron donor) and nitrate into the subsurface, whereas an additional nitrate source exists in the ambient groundwater. Scenarios of stream flow events varying in duration and stream stage are simulated and compared with steady state scenarios with respect to water fluxes, residence times and the solute turn-over rates. Results show, that water exchange and solute turn-over rates highly depend on the interplay between event characteristics and ambient groundwater levels. For scenarios, where the stream flow event shifts the hydraulic system to a net-neutral hydraulic gradient between the average stream stage and the ambient groundwater level (minimal exchange between ground- and surface water), solute consumption is higher, compared to the steady losing or gaining case. In contrast, events that induce strong losing conditions lead to a lower potential of solute consumption.

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

PubMed Central

Zheng, Yao-Rong; Stang, Peter J.

2009-01-01

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

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

PubMed

Zheng, Yao-Rong; Stang, Peter J

2009-03-18

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

Dynamic NMR under nonstationary conditions: Theoretical model, numerical calculation, and potential of application

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

Babailov, S. P., E-mail: babajlov@niic.nsc.ru; National Research Tomsk Polytechnic University, Lenin Avenue 30, Tomsk 634050; Purtov, P. A.

An expression has been derived for the time dependence of the NMR line shape for systems with multi-site chemical exchange in the absence of spin-spin coupling, in a zero saturation limit. The dynamics of variation of the NMR line shape with time is considered in detail for the case of two-site chemical exchange. Mathematical programs have been designed for numerical simulation of the NMR spectra of chemical exchange systems. The analytical expressions obtained are useful for NMR line shape simulations for systems with photoinduced chemical exchange.

14 CFR 65.43 - Rating privileges and exchange.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 14 Aeronautics and Space 2 2010-01-01 2010-01-01 false Rating privileges and exchange. 65.43... § 65.43 Rating privileges and exchange. (a) The holder of a senior rating on August 31, 1970, may at any time after that date exchange his rating for a facility rating at the same air traffic control...

Alteration by hyperoxia of ventilatory dynamics during sinusoidal work.

PubMed

Casaburi, R; Stremel, R W; Whipp, B J; Beaver, W L; Wasserman, K

1980-06-01

The effects of hyperoxia on ventilatory and gas exchange dynamics were studied utilizing sinusoidal work rate forcings. Five subjects exercised on 14 occasions on a cycle ergometer for 30 min with a sinusoidally varying work load. Tests were performed at seven frequencies of work load during air or 100% O2 inspiration. From the breath-by-breath responses to these tests, dynamic characteristics were analyzed by extracting the mean level, amplitude of oscillation, and phase lag for each six variables with digital computer techniques. Calculation of the time constant (tau) of the ventilatory responses demonstrated that ventilatory kinetics were slower during hyperoxia than during normoxia (P less than 0.025; avg 1.56 and 1.13 min, respectively). Further, for identical work rate fluctuations, end-tidal CO2 tension fluctuations were increased by hyperpoxia. Ventilation during hyperoxia is slower to respond to variations in the level of metabolically produced CO2, presumably because hyperoxia attenuates carotid body output; the arterial CO2 tension is consequently less tightly regulated.

Dynamic Response during PEM Fuel Cell Loading-up

PubMed Central

Pei, Pucheng; Yuan, Xing; Gou, Jun; Li, Pengcheng

2009-01-01

A study on the effects of controlling and operating parameters for a Proton Exchange Membrane (PEM) fuel cell on the dynamic phenomena during the loading-up process is presented. The effect of the four parameters of load-up amplitudes and rates, operating pressures and current levels on gas supply or even starvation in the flow field is analyzed based accordingly on the transient characteristics of current output and voltage. Experiments are carried out in a single fuel cell with an active area of 285 cm2. The results show that increasing the loading-up amplitude can inevitably increase the possibility of gas starvation in channels when a constant flow rate has been set for the cathode; With a higher operating pressure, the dynamic performance will be improved and gas starvations can be relieved. The transient gas supply in the flow channel during two loading-up mode has also been discussed. The experimental results will be helpful for optimizing the control and operation strategies for PEM fuel cells in vehicles.

Investigation of Chemical Exchange at Intermediate Exchange Rates using a Combination of Chemical Exchange Saturation Transfer (CEST) and Spin-Locking methods (CESTrho)

PubMed Central

Kogan, Feliks; Singh, Anup; Cai, Keija; Haris, Mohammad; Hariharan, Hari; Reddy, Ravinder

2011-01-01

Proton exchange imaging is important as it allows for visualization and quantification of the distribution of specific metabolites with conventional MRI. Current exchange mediated MRI methods suffer from poor contrast as well as confounding factors that influence exchange rates. In this study we developed a new method to measure proton exchange which combines chemical exchange saturation transfer (CEST) and T1ρ magnetization preparation methods (CESTrho). We demonstrated that this new CESTrho sequence can detect proton exchange in the slow to intermediate exchange regimes. It has a linear dependence on proton concentration which allows it to be used to quantitatively measure changes in metabolite concentration. Additionally, the magnetization scheme of this new method can be customized to make it insensitive to changes in exchange rate while retaining its dependency on solute concentration. Finally, we showed the feasibility of using CESTrho in vivo. This sequence is able to detect proton exchange at intermediate exchange rates and is unaffected by the confounding factors that influence proton exchange rates thus making it ideal for the measurement of metabolites with exchangeable protons in this exchange regime. PMID:22009759

Investigation of chemical exchange at intermediate exchange rates using a combination of chemical exchange saturation transfer (CEST) and spin-locking methods (CESTrho).

PubMed

Kogan, Feliks; Singh, Anup; Cai, Keija; Haris, Mohammad; Hariharan, Hari; Reddy, Ravinder

2012-07-01

Proton exchange imaging is important as it allows for visualization and quantification of the distribution of specific metabolites with conventional MRI. Current exchange mediated MRI methods suffer from poor contrast as well as confounding factors that influence exchange rates. In this study we developed a new method to measure proton exchange which combines chemical exchange saturation transfer and T(1)(ρ) magnetization preparation methods (CESTrho). We demonstrated that this new CESTrho sequence can detect proton exchange in the slow to intermediate exchange regimes. It has a linear dependence on proton concentration which allows it to be used to quantitatively measure changes in metabolite concentration. Additionally, the magnetization scheme of this new method can be customized to make it insensitive to changes in exchange rate while retaining its dependency on solute concentration. Finally, we showed the feasibility of using CESTrho in vivo. This sequence is able to detect proton exchange at intermediate exchange rates and is unaffected by the confounding factors that influence proton exchange rates thus making it ideal for the measurement of metabolites with exchangeable protons in this exchange regime. Copyright © 2011 Wiley Periodicals, Inc.

Carbon dioxide exchange in Norway spruce at the shoot, tree and ecosystem scale.

PubMed

Wallin, G; Linder, S; Lindroth, A; Räntfors, M; Flemberg, S; Grelle, A

2001-08-01

Net CO2 exchange in a 35-year-old boreal Norway spruce (Picea abies (L.) Karst.) forest in northern Sweden was measured at the shoot (NSE), tree (NTE) and ecosystem levels (NEE) by means of shoot cuvettes, whole-tree chambers and the eddy covariance technique, respectively. We compared the dynamics of gross primary production (GPP) at the three levels during the course of a single week. The diurnal dynamics of GPP at each level were estimated by subtracting half-hourly or hourly model-estimated values of total respiration (excluding light-dependent respiration) from net CO(2) exchange. The relationship between temperature and total respiration at each level was derived from nighttime measurements of NSE, NTE and NEE over the course of 1 month. There was a strong linear relationship (r2 = 0.93) between the hourly estimates of GPP at the shoot and tree levels, but the correlation between shoot- and ecosystem-level GPP was weaker (r2 = 0.69). However, the correlation between shoot- and ecosystem-level GPP was improved (r2 = 0.88) if eddy covariance measurements were restricted to periods when friction velocity was > or = 0.5 m s(-1). Daily means were less dependent on friction velocity, giving an r2 value of 0.94 between shoot- and ecosystem-level GPP. The correlation between shoot and tree levels also increased when daily means were compared (r2 = 0.98). Most of the measured variation in carbon exchange rate among the shoot, tree and ecosystem levels was the result of periodic low coupling between vegetation and the atmosphere at the ecosystem level. The results validate the use of measurements at the shoot and tree level for analyzing the contribution of different compartments to net ecosystem CO2 exchange.

Genotypic variation in tolerance to drought stress is highly coordinated with hydraulic conductivity-photosynthesis interplay and aquaporin expression in field-grown mulberry (Morus spp.).

PubMed

Reddy, Kanubothula Sitarami; Sekhar, Kalva Madhana; Reddy, Attipalli Ramachandra

2017-07-01

Hydraulic conductivity quantifies the efficiency of a plant to transport water from root to shoot and is a major constriction on leaf gas exchange physiology. Mulberry (Morus spp.) is the most economically important crop for sericulture industry. In this study, we demonstrate a finely coordinated control of hydraulic dynamics on leaf gas exchange characteristics in 1-year-old field-grown mulberry genotypes (Selection-13 (S13); Kollegal Local (KL) and Kanva-2 (K2)) subjected to water stress by withholding water for 20 days and subsequent recovery for 7 days. Significant variations among three mulberry genotypes have been recorded in net photosynthetic rates (Pn), stomatal conductance and sap flow rate, as well as hydraulic conductivity in stem (KS) and leaf (KL). Among three genotypes, S13 showed significantly high rates of Pn, KS and KL both in control as well as during drought stress (DS) and recovery, providing evidence for superior drought-adaptive strategies. The plant water hydraulics-photosynthesis interplay was finely coordinated with the expression of certain key aquaporins (AQPs) in roots and leaves. Our data clearly demonstrate that expression of certain AQPs play a crucial role in hydraulic dynamics and photosynthetic carbon assimilation during DS and recovery, which could be effectively targeted towards mulberry improvement programs for drought adaptation. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Statistical properties of the yuan exchange rate index

NASA Astrophysics Data System (ADS)

Wang, Dong-Hua; Yu, Xiao-Wen; Suo, Yuan-Yuan

2012-06-01

We choice the yuan exchange rate index based on a basket of currencies as the effective exchange rate of the yuan and investigate the statistical properties of the yuan exchange rate index after China's exchange rate system reform on the 21st July 2005. After dividing the time series into two parts according to the change in the yuan exchange rate regime in July 2008, we compare the statistical properties of the yuan exchange rate index during these two periods. We find that the distribution of the two return series has the exponential form. We also perform the detrending moving average analysis (DMA) and the multifractal detrending moving average analysis (MFDMA). The two periods possess different degrees of long-range correlations, and the multifractal nature is also unveiled in these two time series. Significant difference is found in the scaling exponents τ(q) and singularity spectra f(α) of the two periods obtained from the MFDMA analysis. Besides, in order to detect the sources of multifractality, shuffling and phase randomization procedures are applied to destroy the long-range temporal correlation and fat-tailed distribution of the yuan exchange rate index respectively. We find that the fat-tailedness plays a critical role in the sources of multifractality in the first period, while the long memory is the major cause in the second period. The results suggest that the change in China's exchange rate regime in July 2008 gives rise to the different multifractal properties of the yuan exchange rate index in these two periods, and thus has an effect on the effective exchange rate of the yuan after the exchange rate reform on the 21st July 2005.

Dynamic Histogram Analysis To Determine Free Energies and Rates from Biased Simulations.

PubMed

Stelzl, Lukas S; Kells, Adam; Rosta, Edina; Hummer, Gerhard

2017-12-12

We present an algorithm to calculate free energies and rates from molecular simulations on biased potential energy surfaces. As input, it uses the accumulated times spent in each state or bin of a histogram and counts of transitions between them. Optimal unbiased equilibrium free energies for each of the states/bins are then obtained by maximizing the likelihood of a master equation (i.e., first-order kinetic rate model). The resulting free energies also determine the optimal rate coefficients for transitions between the states or bins on the biased potentials. Unbiased rates can be estimated, e.g., by imposing a linear free energy condition in the likelihood maximization. The resulting "dynamic histogram analysis method extended to detailed balance" (DHAMed) builds on the DHAM method. It is also closely related to the transition-based reweighting analysis method (TRAM) and the discrete TRAM (dTRAM). However, in the continuous-time formulation of DHAMed, the detailed balance constraints are more easily accounted for, resulting in compact expressions amenable to efficient numerical treatment. DHAMed produces accurate free energies in cases where the common weighted-histogram analysis method (WHAM) for umbrella sampling fails because of slow dynamics within the windows. Even in the limit of completely uncorrelated data, where WHAM is optimal in the maximum-likelihood sense, DHAMed results are nearly indistinguishable. We illustrate DHAMed with applications to ion channel conduction, RNA duplex formation, α-helix folding, and rate calculations from accelerated molecular dynamics. DHAMed can also be used to construct Markov state models from biased or replica-exchange molecular dynamics simulations. By using binless WHAM formulated as a numerical minimization problem, the bias factors for the individual states can be determined efficiently in a preprocessing step and, if needed, optimized globally afterward.

Li + solvation and kinetics of Li +–BF 4 -/PF 6 - ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories

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

Chang, Tsun-Mei; Dang, Liem X.

Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine in this paper the ethylene carbonate (EC) exchange process between the first and second solvation shells around Li + and the dissociation kinetics of ion pairs Li +–[BF 4] and Li +–[PF 6] in this solvent. We calculate the exchange rates using transition state theory and correct them with transmission coefficients computed by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found that the residence times of EC around Li + ions varied from 60 to 450 ps, depending on themore » correction method used. We found that the relaxation times changed significantly from Li +–[BF 4] to Li +–[PF 6] ion pairs in EC. Finally, our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influences the dissociation kinetics of ion pairing.« less

Li + solvation and kinetics of Li +–BF 4 -/PF 6 - ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories

DOE PAGES

Chang, Tsun-Mei; Dang, Liem X.

2017-07-19

Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine in this paper the ethylene carbonate (EC) exchange process between the first and second solvation shells around Li + and the dissociation kinetics of ion pairs Li +–[BF 4] and Li +–[PF 6] in this solvent. We calculate the exchange rates using transition state theory and correct them with transmission coefficients computed by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found that the residence times of EC around Li + ions varied from 60 to 450 ps, depending on themore » correction method used. We found that the relaxation times changed significantly from Li +–[BF 4] to Li +–[PF 6] ion pairs in EC. Finally, our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influences the dissociation kinetics of ion pairing.« less

How amide hydrogens exchange in native proteins.

PubMed

Persson, Filip; Halle, Bertil

2015-08-18

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

How amide hydrogens exchange in native proteins

PubMed Central

Persson, Filip; Halle, Bertil

2015-01-01

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

Landau-Lifshitz-Bloch equation for exchange-coupled grains

NASA Astrophysics Data System (ADS)

Vogler, Christoph; Abert, Claas; Bruckner, Florian; Suess, Dieter

2014-12-01

Heat-assisted recording is a promising technique to further increase the storage density in hard disks. Multilayer recording grains with graded Curie temperature is discussed to further assist the write process. Describing the correct magnetization dynamics of these grains, from room temperature to far above the Curie point, during a write process is required for the calculation of bit error rates. We present a coarse-grained approach based on the Landau-Lifshitz-Bloch (LLB) equation to model exchange-coupled grains with low computational effort. The required temperature-dependent material properties such as the zero-field equilibrium magnetization as well as the parallel and normal susceptibilities are obtained by atomistic Landau-Lifshitz-Gilbert simulations. Each grain is described with one magnetization vector. In order to mimic the atomistic exchange interaction between the grains a special treatment of the exchange field in the coarse-grained approach is presented. With the coarse-grained LLB model the switching probability of a recording grain consisting of two layers with graded Curie temperature is investigated in detail by calculating phase diagrams for different applied heat pulses and external magnetic fields.

Encoding quantum information in a stabilized manifold of a superconducting cavity

NASA Astrophysics Data System (ADS)

Touzard, S.; Leghtas, Z.; Mundhada, S. O.; Axline, C.; Reagor, M.; Chou, K.; Blumoff, J.; Sliwa, K. M.; Shankar, S.; Frunzio, L.; Schoelkopf, R. J.; Mirrahimi, M.; Devoret, M. H.

In a superconducting Josephson circuit architecture, we activate a multi-photon process between two modes by applying microwave drives at specific frequencies. This creates a pairwise exchange of photons between a high-Q cavity and the environment. The resulting open dynamical system develops a two-dimensional quasi-energy ground state manifold. Can we encode, protect and manipulate quantum information in this manifold? We experimentally investigate the convergence and escape rates in and out of this confined subspace. Finally, using quantum Zeno dynamics, we aim to perform gates which maintain the state in the protected manifold at all times. Work supported by: ARO, ONR, AFOSR and YINQE.

Solvent Exchange Leading to Nanobubble Nucleation: A Molecular Dynamics Study

PubMed Central

2017-01-01

The solvent exchange procedure has become the most-used protocol to produce surface nanobubbles, while the molecular mechanisms behind the solvent exchange are far from being fully understood. In this paper, we build a simple model and use molecular dynamics simulations to investigate the dynamic characteristics of solvent exchange for producing nanobubbles. We find that at the first stage of solvent exchange, there exists an interface between interchanging solvents of different gas solubility. This interface moves toward the substrate gradually as the exchange process proceeds. Our simulations reveal directed diffusion of gas molecules against the gas concentration gradient, driven by the solubility gradient of the liquid composition across the moving solvent–solvent interface. It is this directed diffusion that causes gas retention and produces a local gas oversaturation much higher near the substrate than far from it. At the second stage of solvent exchange, the high local gas oversaturation leads to bubble nucleation either on the solid surface or in the bulk solution, which is found to depend on the substrate hydrophobicity and the degree of local gas oversaturation. Our findings suggest that solvent exchange could be developed into a standard procedure to produce oversaturation and used to a variety of nucleation applications other than generating nanobubbles. PMID:28742364

High Br- Content CsPb(Cl yBr1- y)3 Perovskite Nanocrystals with Strong Mn2+ Emission through Diverse Cation/Anion Exchange Engineering.

PubMed

Li, Fei; Xia, Zhiguo; Pan, Caofeng; Gong, Yue; Gu, Lin; Liu, Quanlin; Zhang, Jin Z

2018-04-11

The unification of tunable band edge (BE) emission and strong Mn 2+ doping luminescence in all-inorganic cesium lead halide perovskite nanocrystals (NCs) CsPbX 3 (X = Cl and Br) is of fundamental importance in fine tuning their optical properties. Herein, we demonstrate that benefiting from the differentiation of the cation/anion exchange rate, ZnBr 2 and preformed CsPb 1- x Cl 3 : xMn 2+ NCs can be used to obtain high Br - content Cs(Pb 1- x- z Zn z )(Cl y Br 1- y ) 3 : xMn 2+ perovskite NCs with strong Mn 2+ emission, and the Mn 2+ substitution ratio can reach about 22%. More specifically, the fast anion exchange could be realized by the soluble halide precursors, leading to anion exchange within a few seconds as observed from the strong BE emission evolution, whereas the cation exchange instead generally required at least a few hours; moreover, their exchange mechanism and dynamics process have been evaluated. The Mn 2+ emission intensity could be further varied by controlling the replacement of Mn 2+ by Zn 2+ with prolonged ion exchange reaction time. White light emission of the doped perovskite NCs via this cation/anion synergistic exchange strategy has been realized, which was also successfully demonstrated in a prototype white light-emitting diode (LED) device based on a commercially available 365 nm LED chip.

Evaluation of enhanced sampling provided by accelerated molecular dynamics with Hamiltonian replica exchange methods.

PubMed

Roe, Daniel R; Bergonzo, Christina; Cheatham, Thomas E

2014-04-03

Many problems studied via molecular dynamics require accurate estimates of various thermodynamic properties, such as the free energies of different states of a system, which in turn requires well-converged sampling of the ensemble of possible structures. Enhanced sampling techniques are often applied to provide faster convergence than is possible with traditional molecular dynamics simulations. Hamiltonian replica exchange molecular dynamics (H-REMD) is a particularly attractive method, as it allows the incorporation of a variety of enhanced sampling techniques through modifications to the various Hamiltonians. In this work, we study the enhanced sampling of the RNA tetranucleotide r(GACC) provided by H-REMD combined with accelerated molecular dynamics (aMD), where a boosting potential is applied to torsions, and compare this to the enhanced sampling provided by H-REMD in which torsion potential barrier heights are scaled down to lower force constants. We show that H-REMD and multidimensional REMD (M-REMD) combined with aMD does indeed enhance sampling for r(GACC), and that the addition of the temperature dimension in the M-REMD simulations is necessary to efficiently sample rare conformations. Interestingly, we find that the rate of convergence can be improved in a single H-REMD dimension by simply increasing the number of replicas from 8 to 24 without increasing the maximum level of bias. The results also indicate that factors beyond replica spacing, such as round trip times and time spent at each replica, must be considered in order to achieve optimal sampling efficiency.

Survival of extrasolar giant planet moons in planet-planet scattering

NASA Astrophysics Data System (ADS)

CIAN HONG, YU; Lunine, Jonathan; Nicholson, Phillip; Raymond, Sean

2015-12-01

Planet-planet scattering is the best candidate mechanism for explaining the eccentricity distribution of exoplanets. Here we study the survival and dynamics of exomoons under strong perturbations during giant planet scattering. During close encounters, planets and moons exchange orbital angular momentum and energy. The most common outcomes are the destruction of moons by ejection from the system, collision with the planets and the star, and scattering of moons onto perturbed but still planet-bound orbits. A small percentage of interesting moons can remain bound to ejected (free-floating) planets or be captured by a different planet. Moons' survival rate is correlated with planet observables such as mass, semi-major axis, eccentricity and inclination, as well as the close encounter distance and the number of close encounters. In addition, moons' survival rate and dynamical outcomes are predetermined by the moons' initial semi-major axes. The survival rate drops quickly as moons' distances increase, but simulations predict a good chance of survival for the Galilean moons. Moons with different dynamical outcomes occupy different regions of orbital parameter space, which may enable the study of moons' past evolution. Potential effects of planet obliquity evolution caused by close encounters on the satellites’ stability and dynamics will be reported, as well as detailed and systematic studies of individual close encounter events.

Quantifying hyporheic exchange dynamics in a highly regulated large river reach

NASA Astrophysics Data System (ADS)

Zhou, T.; Bao, J.; Huang, M.; Hou, Z.; Arntzen, E.; Mackley, R.; Harding, S.; Crump, A.; Xu, Y.; Song, X.; Chen, X.; Stegen, J.; Hammond, G. E.; Thorne, P. D.; Zachara, J. M.

2016-12-01

Hyporheic exchange is an important mechanism taking place in riverbanks and riverbed sediments, where the river water and shallow groundwater mix and interact with each other. The direction and magnitude of hyporheic flux that penetrates the river bed and residence time of river water in the hyporheic zone are critical for biogeochemical processes such as carbon and nitrogen cycling, and biodegradation of organic contaminants. Hyporheic flux can be quantified using many direct and indirect measurements as well as analytical and numerical modeling tools. However, in a relatively large river, these methods can be limited by the accessibility, spatial constraints, complexity of geomorphologic features and subsurface properties, and computational power. In rivers regulated by hydroelectric dams, quantifying hyporheic fluxes becomes more challenging due to frequent hydropeaking events created by dam operations. In this study, we developed and validated methods that combined field measurements and numerical modeling for estimating hyporheic fluxes across the river bed in a 7-km long reach of the highly regulated Columbia River. The reach has a minimum width of about 800 meters and variations in river stage within a day could be up to two meters due to the upstream dam operations. In shallow water along the shoreline, vertical thermal profiles measured by self-recording thermistors were combined with time series of hydraulic gradient derived from river stage and water level at in-land wells to estimate the hyporheic flux rate. For the deep section, a high resolution computational fluid dynamics (CFD) modeling framework was developed to characterize the spatial distribution of flux rates at the river bed and the residence time of hyporheic flow at different river flow conditions. Our modeling results show that the rates of hyporheic exchange and residence time are controlled by (1) hydrostatic pressure induced by river stage fluctuations, and (2) hydrodynamic drivers associated with flow velocity variations, which also to certain extent dependent on flow conditions.

Molecular dynamics study of thermodynamic stability and dynamics of [Li(glyme)]+ complex in lithium-glyme solvate ionic liquids

NASA Astrophysics Data System (ADS)

Shinoda, Wataru; Hatanaka, Yuta; Hirakawa, Masashi; Okazaki, Susumu; Tsuzuki, Seiji; Ueno, Kazuhide; Watanabe, Masayoshi

2018-05-01

Equimolar mixtures of glymes and organic lithium salts are known to produce solvate ionic liquids, in which the stability of the [Li(glyme)]+ complex plays an important role in determining the ionic dynamics. Since these mixtures have attractive physicochemical properties for application as electrolytes, it is important to understand the dependence of the stability of the [Li(glyme)]+ complex on the ion dynamics. A series of microsecond molecular dynamics simulations has been conducted to investigate the dynamic properties of these solvate ionic liquids. Successful solvate ionic liquids with high stability of the [Li(glyme)]+ complex have been shown to have enhanced ion dynamics. Li-glyme pair exchange rarely occurs: its characteristic time is longer than that of ion diffusion by one or two orders of magnitude. Li-glyme pair exchange most likely occurs through cluster formation involving multiple [Li(glyme)]+ pairs. In this process, multiple exchanges likely take place in a concerted manner without the production of energetically unfavorable free glyme or free Li+ ions.

Boreal peatland pools C release: implication for the contemporary C exchange

NASA Astrophysics Data System (ADS)

Pelletier, L.; Strachan, I. B.; Garneau, M.; Roulet, N. T.

2013-12-01

Peatland ecosystems are considered to be net-sinks for carbon, with long-term accumulation rates ranging between 3 and 71 g C m-2 yr-1. However, the net carbon exchange rates vary significantly across the surface of these ecosystems, both in terms of magnitude and direction of the fluxes. Boreal peatlands are characterized by microforms ranging from dry hummocks, to lawns, to wet hollows and pools, which have distinct physical and chemical properties. While the hummocks and lawns absorb C due to the positive balance between gross primary production (CO2 uptake) and respiration (CO2 and CH4 release), pools represent net sources of carbon to the atmosphere. Annual pool C fluxes have been poorly documented and their contribution to the ecosystem level C budget is often ignored, even if they cover a significant portion of the peatland surface. Furthermore, the net ecosystem CO2 exchange (NEE) of these peatlands remains largely unknown. In this study, we examine the dynamics of the atmospheric exchange of CO2 and CH4 from peatland pools. Dissolved CO2 and CH4 were measured sporadically in five pools using the headspace technique and continuously with an NDIR sensor (CO2 for one pool only) over a 16-month period. Fluxes were calculated using the thin boundary layer model. We measured spring release and growing season (May to October) NEE-CO2 and CH4 fluxes in the same peatland using an eddy covariance tower to see how the presence of pools impacts the contemporary C exchange at the ecosystem level.

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

"Invisible" conformers of an antifungal disulfide protein revealed by constrained cold and heat unfolding, CEST-NMR experiments, and molecular dynamics calculations.

PubMed

Fizil, Ádám; Gáspári, Zoltán; Barna, Terézia; Marx, Florentine; Batta, Gyula

2015-03-23

Transition between conformational states in proteins is being recognized as a possible key factor of function. In support of this, hidden dynamic NMR structures were detected in several cases up to populations of a few percent. Here, we show by two- and three-state analysis of thermal unfolding, that the population of hidden states may weight 20-40 % at 298 K in a disulfide-rich protein. In addition, sensitive (15) N-CEST NMR experiments identified a low populated (0.15 %) state that was in slow exchange with the folded PAF protein. Remarkably, other techniques failed to identify the rest of the NMR "dark matter". Comparison of the temperature dependence of chemical shifts from experiments and molecular dynamics calculations suggests that hidden conformers of PAF differ in the loop and terminal regions and are most similar in the evolutionary conserved core. Our observations point to the existence of a complex conformational landscape with multiple conformational states in dynamic equilibrium, with diverse exchange rates presumably responsible for the completely hidden nature of a considerable fraction. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Dynamic Characteristics of Ventilatory and Gas Exchange during Sinusoidal Walking in Humans.

PubMed

Fukuoka, Yoshiyuki; Iihoshi, Masaaki; Nazunin, Juhelee Tuba; Abe, Daijiro; Fukuba, Yoshiyuki

2017-01-01

Our present study investigated whether the ventilatory and gas exchange responses show different dynamics in response to sinusoidal change in cycle work rate or walking speed even if the metabolic demand was equivalent in both types of exercise. Locomotive parameters (stride length and step frequency), breath-by-breath ventilation (V̇E) and gas exchange (CO2 output (V̇CO2) and O2 uptake (V̇O2)) responses were measured in 10 healthy young participants. The speed of the treadmill was sinusoidally changed between 3 km·h-1 and 6 km·h-1 with various periods (from 10 to 1 min). The amplitude of locomotive parameters against sinusoidal variation showed a constant gain with a small phase shift, being independent of the oscillation periods. In marked contrast, when the periods of the speed oscillations were shortened, the amplitude of V̇E decreased sharply whereas the phase shift of V̇E increased. In comparing walking and cycling at the equivalent metabolic demand, the amplitude of V̇E during sinusoidal walking (SW) was significantly greater than that during sinusoidal cycling (SC), and the phase shift became smaller. The steeper slope of linear regression for the V̇E amplitude ratio to V̇CO2 amplitude ratio was observed during SW than SC. These findings suggested that the greater amplitude and smaller phase shift of ventilatory dynamics were not equivalent between SW and SC even if the metabolic demand was equivalent between both exercises. Such phenomenon would be derived from central command in proportion to locomotor muscle recruitment (feedforward) and muscle afferent feedback.

Very Tiny Rocks: Site-Specific, Size-Dependent Reaction Kinetics at Nanoparticle-Water Interfaces

NASA Astrophysics Data System (ADS)

Rustad, J. R.

2008-12-01

One of the most fundamental challenges in geochemistry is to be able to understand the rates and mechanisms of elementary reactions that describe chemical processes occurring at mineral-water interfaces. One of the reasons for the primitive conceptual state of reaction kinetics in solid earth geochemistry is that it is very difficult to identify defensible elementary reactions where theoretical predictions can be made and the results can tested experimentally at the same length and time scale of the prediction. For example, the most fundamental predictor of complexation kinetics in aqueous solution is the characteristic water exchange rate, which are well known for the aquo ions and vary by 20 orders of magnitude even for simple trivalent ions. In contrast, for interfacial reactions, it was not even known whether water exchange rates were faster or slower than equivalent metal sites in solution, prohibiting any quantitive understanding of mineral reaction kinetics at the molecular level. Recent advances in synthesis and characterization of materials at nanometer length scales has been able to bridge the gap in scale, and nanometer-sized minerals have given us our first quantitative understanding of elementary reaction rates for fundamental processes involving water and hydroxide exchange reactions. I describe the results of molecular dynamics calculation and experimental measurement of the rates of water, hydroxide, and proton exchange reactions on nanoparticle surfaces. The calculations already show that transition state theory is completely inadequate to understand the rates of even the simplest elementary reactions. Furthermore, the mechanistic implications of rate parameters such as activation volume and activation enthalpy may be different in moving from aquo ions to interfaces. Is a molecular understanding of geochemical processes really needed? One might have asked a biologist at the turn of the century whether studying the structure of proteins would ever be useful for curing disease. True molecular level understanding of interfacial interactions has the potential to revolutionize geology, allowing unprecedented detail and accuracy in such important contexts as climate reconstruction and tectonic history. Geology has an inevitable molecular future.

Triangular arbitrage as an interaction among foreign exchange rates

NASA Astrophysics Data System (ADS)

Aiba, Yukihiro; Hatano, Naomichi; Takayasu, Hideki; Marumo, Kouhei; Shimizu, Tokiko

2002-07-01

We first show that there are in fact triangular arbitrage opportunities in the spot foreign exchange markets, analyzing the time dependence of the yen-dollar rate, the dollar-euro rate and the yen-euro rate. Next, we propose a model of foreign exchange rates with an interaction. The model includes effects of triangular arbitrage transactions as an interaction among three rates. The model explains the actual data of the multiple foreign exchange rates well.

Free energy surface of an intrinsically disordered protein: comparison between temperature replica exchange molecular dynamics and bias-exchange metadynamics.

PubMed

Zerze, Gül H; Miller, Cayla M; Granata, Daniele; Mittal, Jeetain

2015-06-09

Intrinsically disordered proteins (IDPs), which are expected to be largely unstructured under physiological conditions, make up a large fraction of eukaryotic proteins. Molecular dynamics simulations have been utilized to probe structural characteristics of these proteins, which are not always easily accessible to experiments. However, exploration of the conformational space by brute force molecular dynamics simulations is often limited by short time scales. Present literature provides a number of enhanced sampling methods to explore protein conformational space in molecular simulations more efficiently. In this work, we present a comparison of two enhanced sampling methods: temperature replica exchange molecular dynamics and bias exchange metadynamics. By investigating both the free energy landscape as a function of pertinent order parameters and the per-residue secondary structures of an IDP, namely, human islet amyloid polypeptide, we found that the two methods yield similar results as expected. We also highlight the practical difference between the two methods by describing the path that we followed to obtain both sets of data.

Search for a new exchange-rate regime.

PubMed

Williamson, J

1987-07-31

The regime of unmanaged floating exchange rates was implicitly judged a failure when, with the Plaza Agreement, attempts at cooperative exchange-rate management were reintroduced primarily because of concern at the size of misalignments. Any satisfactory successor regime will need to limit misalignments while retaining the genuine social benefits of exchange-rate flexibility. It is argued that a system of target zones for exchange rates, ideally embedded in a more comprehensive set of guidelines for international economic policy coordination, could best reconcile these needs.

Modeling inflation rates and exchange rates in Ghana: application of multivariate GARCH models.

PubMed

Nortey, Ezekiel Nn; Ngoh, Delali D; Doku-Amponsah, Kwabena; Ofori-Boateng, Kenneth

2015-01-01

This paper was aimed at investigating the volatility and conditional relationship among inflation rates, exchange rates and interest rates as well as to construct a model using multivariate GARCH DCC and BEKK models using Ghana data from January 1990 to December 2013. The study revealed that the cumulative depreciation of the cedi to the US dollar from 1990 to 2013 is 7,010.2% and the yearly weighted depreciation of the cedi to the US dollar for the period is 20.4%. There was evidence that, the fact that inflation rate was stable, does not mean that exchange rates and interest rates are expected to be stable. Rather, when the cedi performs well on the forex, inflation rates and interest rates react positively and become stable in the long run. The BEKK model is robust to modelling and forecasting volatility of inflation rates, exchange rates and interest rates. The DCC model is robust to model the conditional and unconditional correlation among inflation rates, exchange rates and interest rates. The BEKK model, which forecasted high exchange rate volatility for the year 2014, is very robust for modelling the exchange rates in Ghana. The mean equation of the DCC model is also robust to forecast inflation rates in Ghana.

Physical Forces between Humans and How Humans Attract and Repel Each Other Based on Their Social Interactions in an Online World

PubMed Central

Thurner, Stefan; Fuchs, Benedikt

2015-01-01

Physical interactions between particles are the result of the exchange of gauge bosons. Human interactions are mediated by the exchange of messages, goods, money, promises, hostilities, etc. While in the physical world interactions and their associated forces have immediate dynamical consequences (Newton’s laws) the situation is not clear for human interactions. Here we quantify the relative acceleration between humans who interact through the exchange of messages, goods and hostilities in a massive multiplayer online game. For this game we have complete information about all interactions (exchange events) between about 430,000 players, and about their trajectories (movements) in the metric space of the game universe at any point in time. We use this information to derive “interaction potentials" for communication, trade and attacks and show that they are harmonic in nature. Individuals who exchange messages and trade goods generally attract each other and start to separate immediately after exchange events end. The form of the interaction potential for attacks mirrors the usual “hit-and-run" tactics of aggressive players. By measuring interaction intensities as a function of distance, velocity and acceleration, we show that “forces" between players are directly related to the number of exchange events. We find an approximate power-law decay of the likelihood for interactions as a function of distance, which is in accordance with previous real world empirical work. We show that the obtained potentials can be understood with a simple model assuming an exchange-driven force in combination with a distance-dependent exchange rate. PMID:26196505

Physical Forces between Humans and How Humans Attract and Repel Each Other Based on Their Social Interactions in an Online World.

PubMed

Thurner, Stefan; Fuchs, Benedikt

2015-01-01

Physical interactions between particles are the result of the exchange of gauge bosons. Human interactions are mediated by the exchange of messages, goods, money, promises, hostilities, etc. While in the physical world interactions and their associated forces have immediate dynamical consequences (Newton's laws) the situation is not clear for human interactions. Here we quantify the relative acceleration between humans who interact through the exchange of messages, goods and hostilities in a massive multiplayer online game. For this game we have complete information about all interactions (exchange events) between about 430,000 players, and about their trajectories (movements) in the metric space of the game universe at any point in time. We use this information to derive "interaction potentials" for communication, trade and attacks and show that they are harmonic in nature. Individuals who exchange messages and trade goods generally attract each other and start to separate immediately after exchange events end. The form of the interaction potential for attacks mirrors the usual "hit-and-run" tactics of aggressive players. By measuring interaction intensities as a function of distance, velocity and acceleration, we show that "forces" between players are directly related to the number of exchange events. We find an approximate power-law decay of the likelihood for interactions as a function of distance, which is in accordance with previous real world empirical work. We show that the obtained potentials can be understood with a simple model assuming an exchange-driven force in combination with a distance-dependent exchange rate.

12 CFR 1750.2 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-01-01

... Mortgage Corporation and any affiliate thereof. Foreign exchange rate contracts— (1) Means cross-currency interest rate swaps, forward foreign exchange contracts, currency options purchased (including currency... less and foreign exchange rate contracts traded on exchanges that require daily payment of variation...

Structural Dynamics in Ras and Related Proteins upon Nucleotide Switching.

PubMed

Harrison, Rane A; Lu, Jia; Carrasco, Martin; Hunter, John; Manandhar, Anuj; Gondi, Sudershan; Westover, Kenneth D; Engen, John R

2016-11-20

Structural dynamics of Ras proteins contributes to their activity in signal transduction cascades. Directly targeting Ras proteins with small molecules may rely on the movement of a conserved structural motif, switch II. To understand Ras signaling and advance Ras-targeting strategies, experimental methods to measure Ras dynamics are required. Here, we demonstrate the utility of hydrogen-deuterium exchange (HDX) mass spectrometry (MS) to measure Ras dynamics by studying representatives from two branches of the Ras superfamily, Ras and Rho. A comparison of differential deuterium exchange between active (GMPPNP-bound) and inactive (GDP-bound) proteins revealed differences between the families, with the most notable differences occurring in the phosphate-binding loop and switch II. The P-loop exchange signature correlated with switch II dynamics observed in molecular dynamics simulations focused on measuring main-chain movement. HDX provides a means of evaluating Ras protein dynamics, which may be useful for understanding the mechanisms of Ras signaling, including activated signaling of pathologic mutants, and for targeting strategies that rely on protein dynamics. Copyright © 2016 Elsevier Ltd. All rights reserved.

Static Modulation Wave of Arrays of Halogen Interactions Transduced to a Hierarchy of Nanoscale Change Stimuli of Crystalline Rotors Dynamics.

PubMed

Simonov, Sergey; Zorina, Leokadiya; Wzietek, Pawel; Rodríguez-Fortea, Antonio; Canadell, Enric; Mézière, Cécile; Bastien, Guillaume; Lemouchi, Cyprien; Garcia-Garibay, Miguel A; Batail, Patrick

2018-06-13

Here we present a study where what can be seen as a static modulation wave encompassing four successive arrays of interacting iodine atoms in crystalline 1,4-Bis((4'-(iodoethynyl)phenyl) ethynyl)bicyclo[2,2,2]octane rotors changes the structure from one-half molecule to three-and-a-half molecules in the asymmetric unit below a phase transition at 105 K. The remarkable finding is that the total 1 H spin-lattice relaxation rate, T 1 -1 , of unprecedented complexity to date in molecular rotors, is the weighted sum of the relaxation rates of the four contributing rotors relaxation rates, each with distinguishable exchange frequencies reflecting Arrhenius parameters with different activation barriers ( E a ) and attempt frequencies (τ o -1 ). This allows us to show in tandem with rotor-environment interaction energy calculations how the dynamics of molecular rotors are able to decode structural information from their surroundings with remarkable nanoscale precision.

Forecasting Foreign Currency Exchange Rates for Air Force Budgeting

DTIC Science & Technology

2015-03-26

FORECASTING FOREIGN CURRENCY EXCHANGE RATES FOR AIR FORCE BUDGETING THESIS MARCH 2015...States. AFIT-ENV-MS-15-M-178 FORECASTING FOREIGN CURRENCY EXCHANGE RATES FOR AIR FORCE BUDGETING THESIS Presented to the Faculty...FORECASTING FOREIGN CURRENCY EXCHANGE RATES FOR AIR FORCE BUDGETING Nicholas R. Gardner, BS Captain, USAF Committee Membership: Lt Col Jonathan

Testing for Marshall-Lerner hypothesis: A panel approach

NASA Astrophysics Data System (ADS)

Azizan, Nur Najwa; Sek, Siok Kun

2014-12-01

The relationship between real exchange rate and trade balances are documented in many theories. One of the theories is the so-called Marshall-Lerner condition. In this study, we seek to test for the validity of Marshall-Lerner hypothesis, i.e. to reveal if the depreciation of real exchange rate leads to the improvement in trade balances. We focus our study in ASEAN-5 countries and their main trade partners of U.S., Japan and China. The dynamic panel data of pooled mean group (PMG) approach is used to detect the Marshall-Lerner hypothesis among ASEAN-5, between ASEAN-5 and U.S., between ASEAN-5 and Japan and between ASEAN-5 and China respectively. The estimation is based on the autoregressive Distributed Lag or ARDL model for the period of 1970-2012. The paper concludes that Marshal Lerner theory does not hold in bilateral trades in four groups of countries. The trade balances of ASEAN5 are mainly determined by the domestic income level and foreign production cost.

World currency exchange rate cross-correlations

NASA Astrophysics Data System (ADS)

Droå¼dż, S.; Górski, A. Z.; Kwapień, J.

2007-08-01

World currency network constitutes one of the most complex structures that is associated with the contemporary civilization. On a way towards quantifying its characteristics we study the cross correlations in changes of the daily foreign exchange rates within the basket of 60 currencies in the period December 1998 May 2005. Such a dynamics turns out to predominantly involve one outstanding eigenvalue of the correlation matrix. The magnitude of this eigenvalue depends however crucially on which currency is used as a base currency for the remaining ones. Most prominent it looks from the perspective of a peripheral currency. This largest eigenvalue is seen to systematically decrease and thus the structure of correlations becomes more heterogeneous, when more significant currencies are used as reference. An extreme case in this later respect is the USD in the period considered. Besides providing further insight into subtle nature of complexity, these observations point to a formal procedure that in general can be used for practical purposes of measuring the relative currencies significance on various time horizons.

Analysis of bubbles and crashes in the TRY/USD, TRY/EUR, TRY/JPY and TRY/CHF exchange rate within the scope of econophysics

NASA Astrophysics Data System (ADS)

Deviren, Bayram; Kocakaplan, Yusuf; Keskin, Mustafa; Balcılar, Mehmet; Özdemir, Zeynel Abidin; Ersoy, Ersan

2014-09-01

In this study, we analyze the Turkish Lira/US Dollar (TRY/USD), Turkish Lira/Euro (TRY/EUR), Turkish Lira/Japanese Yen (TRY/JPY) and Turkish Lira/Swiss Franc (TRY/CHF) exchange rates in the global financial crisis period to detect the bubbles and crashes in the TRY by using a mathematical methodology developed by Watanabe et al. (2007). The methodology defines the bubbles and crashes in financial market price fluctuations by considering an exponential fitting of the associated data. This methodology is applied to detect the bubbles and crashes in the TRY/USD, TRY/EUR, TRY/JPY and TRY/CHF exchange rates from January, 1, 2005 to December, 20, 2013. In this mathematical methodology, the whole period of bubbles and crashes can be determined purely from past data, and the start of bubbles and crashes can be identified even before its bursts. In this way, the periods of bubbles and crashes in the TRY/USD, TRY/EUR, TRY/JPY and TRY/CHF are determined, and the beginning and end points of these periods are detected. The results show that the crashes in the TRY/CHF exchange rate are commonly finished earlier than in the other exchange rates; hence it is probable that the crashes in the other exchange rates would be finished soon when the crashes in the TRY/CHF exchange rate ended. We also find that the periods of crashes in the TRY/EUR exchange rate take longer time than in the other exchange rates. This information can be used in risk management and/or speculative gain. The crashes' periods in the TRY/EUR and TRY/USD exchange rates are observed to be relatively longer than in the other exchange rates.

Exploring knowledge exchange: a useful framework for practice and policy.

PubMed

Ward, Vicky; Smith, Simon; House, Allan; Hamer, Susan

2012-02-01

Knowledge translation is underpinned by a dynamic and social knowledge exchange process but there are few descriptions of how this unfolds in practice settings. This has hampered attempts to produce realistic and useful models to help policymakers and researchers understand how knowledge exchange works. This paper reports the results of research which investigated the nature of knowledge exchange. We aimed to understand whether dynamic and fluid definitions of knowledge exchange are valid and to produce a realistic, descriptive framework of knowledge exchange. Our research was informed by a realist approach. We embedded a knowledge broker within three service delivery teams across a mental health organisation in the UK, each of whom was grappling with specific challenges. The knowledge broker participated in the team's problem-solving process and collected observational fieldnotes. We also interviewed the team members. Observational and interview data were analysed quantitatively and qualitatively in order to determine and describe the nature of the knowledge exchange process in more detail. This enabled us to refine our conceptual framework of knowledge exchange. We found that knowledge exchange can be understood as a dynamic and fluid process which incorporates distinct forms of knowledge from multiple sources. Quantitative analysis illustrated that five broadly-defined components of knowledge exchange (problem, context, knowledge, activities, use) can all be in play at any one time and do not occur in a set order. Qualitative analysis revealed a number of distinct themes which better described the nature of knowledge exchange. By shedding light on the nature of knowledge exchange, our findings problematise some of the linear, technicist approaches to knowledge translation. The revised model of knowledge exchange which we propose here could therefore help to reorient thinking about knowledge exchange and act as a starting point for further exploration and evaluation of the knowledge exchange process. Copyright © 2011 Elsevier Ltd. All rights reserved.

Characterizing slow chemical exchange in nucleic acids by carbon CEST and low spin-lock field R(1ρ) NMR spectroscopy.

PubMed

Zhao, Bo; Hansen, Alexandar L; Zhang, Qi

2014-01-08

Quantitative characterization of dynamic exchange between various conformational states provides essential insights into the molecular basis of many regulatory RNA functions. Here, we present an application of nucleic-acid-optimized carbon chemical exchange saturation transfer (CEST) and low spin-lock field R(1ρ) relaxation dispersion (RD) NMR experiments in characterizing slow chemical exchange in nucleic acids that is otherwise difficult if not impossible to be quantified by the ZZ-exchange NMR experiment. We demonstrated the application on a 47-nucleotide fluoride riboswitch in the ligand-free state, for which CEST and R(1ρ) RD profiles of base and sugar carbons revealed slow exchange dynamics involving a sparsely populated (p ~ 10%) and shortly lived (τ ~ 10 ms) NMR "invisible" state. The utility of CEST and low spin-lock field R(1ρ) RD experiments in studying slow exchange was further validated in characterizing an exchange as slow as ~60 s(-1).

Characterizing Slow Chemical Exchange in Nucleic Acids by Carbon CEST and Low Spin-Lock Field R1ρ NMR Spectroscopy

PubMed Central

Zhao, Bo; Hansen, Alexandar L.; Zhang, Qi

2016-01-01

Quantitative characterization of dynamic exchange between various conformational states provides essential insights into the molecular basis of many regulatory RNA functions. Here, we present an application of nucleic-acid-optimized carbon chemical exchange saturation transfer (CEST) and low spin-lock field R1ρ relaxation dispersion (RD) NMR experiments in characterizing slow chemical exchange in nucleic acids that is otherwise difficult if not impossible to be quantified by the ZZ-exchange NMR experiment. We demonstrated the application on a 47-nucleotide fluoride riboswitch in the ligand-free state, for which CEST and R1ρ RD profiles of base and sugar carbons revealed slow exchange dynamics involving a sparsely populated (p ~ 10%) and shortly lived (τ ~ 10 ms) NMR “invisible” state. The utility of CEST and low spin-lock field R1ρ RD experiments in studying slow exchange was further validated in characterizing an exchange as slow as ~60 s−1. PMID:24299272

Patterns of structural dynamics in RACK1 protein retained throughout evolution: A hydrogen-deuterium exchange study of three orthologs

PubMed Central

Tarnowski, Krzysztof; Fituch, Kinga; Szczepanowski, Roman H; Dadlez, Michal; Kaus-Drobek, Magdalena

2014-01-01

RACK1 is a member of the WD repeat family of proteins and is involved in multiple fundamental cellular processes. An intriguing feature of RACK1 is its ability to interact with at least 80 different protein partners. Thus, the structural features enabling such interactomic flexibility are of great interest. Several previous studies of the crystal structures of RACK1 orthologs described its detailed architecture and confirmed predictions that RACK1 adopts a seven-bladed β-propeller fold. However, this did not explain its ability to bind to multiple partners. We performed hydrogen-deuterium (H-D) exchange mass spectrometry on three orthologs of RACK1 (human, yeast, and plant) to obtain insights into the dynamic properties of RACK1 in solution. All three variants retained similar patterns of deuterium uptake, with some pronounced differences that can be attributed to RACK1's divergent biological functions. In all cases, the most rigid structural elements were confined to B-C turns and, to some extent, strands B and C, while the remaining regions retained much flexibility. We also compared the average rate constants for H-D exchange in different regions of RACK1 and found that amide protons in some regions exchanged at least 1000-fold faster than in others. We conclude that its evolutionarily retained structural architecture might have allowed RACK1 to accommodate multiple molecular partners. This was exemplified by our additional analysis of yeast RACK1 dimer, which showed stabilization, as well as destabilization, of several interface regions upon dimer formation. PMID:24591271

Dynamics and unsteady morphologies at ice interfaces driven by D2O–H2O exchange

PubMed Central

Holmes-Cerfon, Miranda; Kohn, Robert V.

2017-01-01

The growth dynamics of D2O ice in liquid H2O in a microfluidic device were investigated between the melting points of D2O ice (3.8 °C) and H2O ice (0 °C). As the temperature was decreased at rates between 0.002 °C/s and 0.1 °C/s, the ice front advanced but retreated immediately upon cessation of cooling, regardless of the temperature. This is a consequence of the competition between diffusion of H2O into the D2O ice, which favors melting of the interface, and the driving force for growth supplied by cooling. Raman microscopy tracked H/D exchange across the solid H2O–solid D2O interface, with diffusion coefficients consistent with transport of intact H2O molecules at the D2O ice interface. At fixed temperatures below 3 °C, the D2O ice front melted continuously, but at temperatures near 0 °C a scalloped interface morphology appeared with convex and concave sections that cycled between growth and retreat. This behavior, not observed for D2O ice in contact with D2O liquid or H2O ice in contact with H2O liquid, reflects a complex set of cooperative phenomena, including H/D exchange across the solid–liquid interface, latent heat exchange, local thermal gradients, and the Gibbs–Thomson effect on the melting points of the convex and concave features. PMID:29042511

Inorganic Carbon and Oxygen Dynamics in a Marsh-dominated Estuary

NASA Astrophysics Data System (ADS)

Wang, S. R.; Di Iorio, D.; Cai, W. J.; Hopkinson, C.

2017-12-01

A free-water mass balance-based study was conducted to address the rate of metabolism and net carbon exchange for the tidal wetland and estuarine portion of the coastal ocean and the uncertainties associated with this approach were assessed. Open water diurnal O2 and dissolved inorganic carbon (DIC) were measured seasonally in a salt marsh-estuary in Georgia, U.S.A. with a focus on the marsh-estuary linkage associated with tidal flooding. We observed that the overall estuarine system was a net source of CO2 to the atmosphere and coastal ocean and a net sink for oceanic and atmospheric O2. Rates of metabolism were extremely high, with respiration (43 mol m-2 yr-1) greatly exceeding gross primary production (28 mol m-2 yr-1), such that the overall system was net heterotrophic. Metabolism measured with DIC were higher than with O2, which we attribute to high rates of anaerobic respiration and reduced sulfur storage in salt marsh sediments, and we assume substantial levels of anoxygenic photosynthesis. We found gas exchange from a flooded marsh is substantial, accounting for about 28% of total O2 and CO2 air-water exchange. A significant percentage of the overall estuarine aquatic metabolism is attributable to metabolism of marsh organisms during inundation. Our study suggests not rely on oceanographic stoichiometry to convert from O2to C based measurements when constructing C balances for the coastal ocean. We also suggest eddy covariance measurements of salt marsh net ecosystem exchange underestimate net ecosystem production as they do not account for lateral DIC exchange associated with marsh tidal inundation. With the increase of global temperature and sea level rise, salt marshes are likely to export more inorganic carbon to the atmosphere and the coastal ocean due to the decrease of solubility, the increase of aquatic and benthic metabolic activities and the longer marsh inundation.

[The conformational dynamics of the tetramer hemoglobin molecule as revealed by hydrogen exchange. III. Influence of the heme removal].

PubMed

Abaturov, L V; Nosova, N G; Shliapnikova, S V

2006-01-01

Two main types of conformational fluctuations--local and global are characteristic of the native protein structure and revealed by hydrogen exchange. The probability of those fluctuations changes to a different extent upon hemoglobin oxygenation, changing of pH, splitting of the intersubunit contacts. To compare with the influence of the heme removal the rate of the H-D exchange of the peptide NH atoms of the human apoHb was studied at the pH range 5.5-9.0 and temperature 10-38 degrees C by the IR spectroscopy. The removal of the heme increases the rate of the H-D exchange of the 80% peptide NH atoms with the factor retardation of the exchange rate (P) in the range approximately 10(2)-10(8). For the most of the peptide NH atoms the probability of the local fluctuations weakly depends on the temperature, the enthalpy changes upon all such local conformational transitions deltaH(op) degrees are 0-15 kcal/M. Characterized by the stronger temperature dependence the global fluctuations are not arised upon the temperature increases up to 38 degrees C at pH 7.0 inspite of in these conditions the slow denaturation and aggregation of apoHb begin to occur. Upon the destabilization of the apoHb structure by the simultaneous decreasing of pH to 5.5 and temperature to 10 degrees C the global fluctuations of the apoHb native structure described by deltaH(op)o < 0 begin to intensify. The mechanism of the overall intensification of the local fluctuations upon the heme removal, the peculiarity of the heat denaturation of apoHb in conditions, close to that existing upon the selfassembly of Hb in vivo, and analogy between low temperature global fluctuations and cold denaturation of globular proteins are discussed.

Report on SNL RCBC control options

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

Ponciroli, R.; Vilim, R. B.

The attractive performance of the S-CO 2 recompression cycle arises from the thermo-physical properties of carbon dioxide near the critical point. However, to ensure efficient operation of the cycle near the critical point, precise control of the heat removal rate by the Printed Circuit Heat Exchanger (PCHE) upstream of the main compressor is required. Accomplishing this task is not trivial because of the large variations in fluid properties with respect to temperature and pressure near the critical point. The use of a model-based approach for the design of a robust feedback regulator is being investigated to achieve acceptable control ofmore » heat removal rate at different operating conditions. A first step in this procedure is the development of a dynamic model of the heat exchanger. In this work, a one-dimensional (1-D) control-oriented model of the PCHE was developed using the General Plant Analyzer and System Simulator (GPASS) code. GPASS is a transient simulation code that supports analysis and control of power conversion cycles based on the S-CO 2 Brayton cycle. This modeling capability was used this fiscal year to analyze experiment data obtained from the heat exchanger in the SNL recompression Brayton cycle. The analysis suggested that the error in the water flowrate measurement was greater than required for achieving precise control of heat removal rate. Accordingly, a new water flowmeter was installed, significantly improving the quality of the measurement. Comparison of heat exchanger measurements in subsequent experiments with code simulations yielded good agreement establishing a reliable basis for the use of the GPASS PCHE model for future development of a model-based feedback controller.« less

A New Approach to Quantify Shallow Water Hydrologic Exchanges in a Large Regulated River Reach

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

Zhou, Tian; Huang, Maoyi; Bao, Jie

Hyporheic exchange is a crucial component in the water cycle. The strength of the exchange directly affects the biogeochemical and ecological processes occurred in the hyporheic zone from micro to reach scale. Hyporheic fluxes can be quantified using many direct and indirect measurements as well as analytical and numerical modeling tools. However, in a relatively large river, these methods are limited by accessibility, the difficulty of performing representative sampling, and complexity of geomorphologic features and subsurface properties. In rivers regulated by hydroelectric dams, quantifying hyporheic fluxes becomes more challenging due to frequent hydropeaking events, featured by hourly to daily variationsmore » in flow and river stages created by dam operations(Hancock 2002). In this study, we developed and validated methods that based on field measurements to estimate shallow water hyporheic fluxes across the river bed at five locations along the shoreline of the Columbia River. Vertical thermal profiles measured by self-recording thermistors were combined with time series of hydraulic gradients derived from river stage and water level at in-land wells to estimate the hyporheic flux rate. The results suggested that the hyporheic exchange rate had high spatial and temporal heterogeneities over the riverbed, with predicted flux rate varies from +1×10 -6 m s-1 to -1.5×10 -6 m s -1 under various flow conditions at the some locations, and with a magnitude of fluxes 6-9 times higher in the primary channel than that in the secondary channel. Furthermore, the variations on shallow water hyporheic flow dynamics may further lead to different biogeochemical and ecological consequences at different river segments.« less

A New Approach to Quantify Shallow Water Hydrologic Exchanges in a Large Regulated River Reach

DOE PAGES

Zhou, Tian; Huang, Maoyi; Bao, Jie; ...

2017-09-15

Hyporheic exchange is a crucial component in the water cycle. The strength of the exchange directly affects the biogeochemical and ecological processes occurred in the hyporheic zone from micro to reach scale. Hyporheic fluxes can be quantified using many direct and indirect measurements as well as analytical and numerical modeling tools. However, in a relatively large river, these methods are limited by accessibility, the difficulty of performing representative sampling, and complexity of geomorphologic features and subsurface properties. In rivers regulated by hydroelectric dams, quantifying hyporheic fluxes becomes more challenging due to frequent hydropeaking events, featured by hourly to daily variationsmore » in flow and river stages created by dam operations(Hancock 2002). In this study, we developed and validated methods that based on field measurements to estimate shallow water hyporheic fluxes across the river bed at five locations along the shoreline of the Columbia River. Vertical thermal profiles measured by self-recording thermistors were combined with time series of hydraulic gradients derived from river stage and water level at in-land wells to estimate the hyporheic flux rate. The results suggested that the hyporheic exchange rate had high spatial and temporal heterogeneities over the riverbed, with predicted flux rate varies from +1×10 -6 m s-1 to -1.5×10 -6 m s -1 under various flow conditions at the some locations, and with a magnitude of fluxes 6-9 times higher in the primary channel than that in the secondary channel. Furthermore, the variations on shallow water hyporheic flow dynamics may further lead to different biogeochemical and ecological consequences at different river segments.« less

26 CFR 1.989(b)-1 - Definition of weighted average exchange rate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 26 Internal Revenue 10 2010-04-01 2010-04-01 false Definition of weighted average exchange rate. 1... (CONTINUED) INCOME TAX (CONTINUED) INCOME TAXES Export Trade Corporations § 1.989(b)-1 Definition of weighted average exchange rate. For purposes of section 989(b)(3) and (4), the term “weighted average exchange rate...

78 FR 15076 - Self-Regulatory Organizations; Chicago Board Options Exchange, Incorporated; Notice of Filing and...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-03-08

... Exchange's proprietary index options products, and the Proprietary Index Options Rate Table will apply to SPXPM (as such, SPXPM, like SPX, will be excluded from the Exchange's other Index Options Rate Table... follows (all listed rates are per contract): \\4\\ See Exchange Fees Schedule, Index Options Rate Table--All...

Heterogeneous effects of oil shocks on exchange rates: evidence from a quantile regression approach.

PubMed

Su, Xianfang; Zhu, Huiming; You, Wanhai; Ren, Yinghua

2016-01-01

The determinants of exchange rates have attracted considerable attention among researchers over the past several decades. Most studies, however, ignore the possibility that the impact of oil shocks on exchange rates could vary across the exchange rate returns distribution. We employ a quantile regression approach to address this issue. Our results indicate that the effect of oil shocks on exchange rates is heterogeneous across quantiles. A large US depreciation or appreciation tends to heighten the effects of oil shocks on exchange rate returns. Positive oil demand shocks lead to appreciation pressures in oil-exporting countries and this result is robust across lower and upper return distributions. These results offer rich and useful information for investors and decision-makers.

The Dynamics of Social Interaction in Telecollaborative Tandem Exchanges

ERIC Educational Resources Information Center

Janssen Sanchez, Brianna

2015-01-01

Using both quantitative and qualitative methods of inquiry, this dissertation study undertakes an exploration of the dynamics of the social interaction in discourse co-constructed by pairs of college students in telecollaborative tandem exchanges. Two groups of participants, Mexican learners of English as a foreign language and American learners…

Linking nonstructural carbohydrate dynamics to gas exchange and leaf hydraulic behavior in Pinus edulis and Juniperus monosperma

Treesearch

David R. Woodruff; Frederick C. Meinzer; Danielle E. Marias; Sanna Sevanto; Michael W. Jenkins; Nate G. McDowell

2014-01-01

Leaf hydraulics, gas exchange and carbon storage in Pinus edulis and Juniperus monosperma, two tree species on opposite ends of the isohydry–anisohydry spectrum, were analyzed to examine relationships between hydraulic function and carbohydrate dynamics.Leaf hydraulic vulnerability,...

Implementation of Dynamic Extensible Adaptive Locally Exchangeable Measures (IDEALEM) v 0.1

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

Sim, Alex; Lee, Dongeun; Wu, K. John

2016-03-04

Handling large streaming data is essential for various applications such as network traffic analysis, social networks, energy cost trends, and environment modeling. However, it is in general intractable to store, compute, search, and retrieve large streaming data. This software addresses a fundamental issue, which is to reduce the size of large streaming data and still obtain accurate statistical analysis. As an example, when a high-speed network such as 100 Gbps network is monitored, the collected measurement data rapidly grows so that polynomial time algorithms (e.g., Gaussian processes) become intractable. One possible solution to reduce the storage of vast amounts ofmore » measured data is to store a random sample, such as one out of 1000 network packets. However, such static sampling methods (linear sampling) have drawbacks: (1) it is not scalable for high-rate streaming data, and (2) there is no guarantee of reflecting the underlying distribution. In this software, we implemented a dynamic sampling algorithm, based on the recent technology from the relational dynamic bayesian online locally exchangeable measures, that reduces the storage of data records in a large scale, and still provides accurate analysis of large streaming data. The software can be used for both online and offline data records.« less

Sensitivity of mesquite shrubland CO2 exchange to precipitation in contrasting landscape settings.

PubMed

Potts, Daniel L; Scott, Russell L; Cable, Jessica M; Huxman, Travis E; Williams, David G

2008-10-01

In semiarid ecosystems, physiography (landscape setting) may interact with woody-plant and soil microbe communities to constrain seasonal exchanges of material and energy at the ecosystem scale. In an upland and riparian shrubland, we examined the seasonally dynamic linkage between ecosystem CO2 exchange, woody-plant water status and photosynthesis, and soil respiration responses to summer rainfall. At each site, we compared tower-based measurements of net ecosystem CO2 exchange (NEE) with ecophysiological measurements among velvet mesquite (Prosopis velutina Woot.) in three size classes and soil respiration in sub-canopy and inter-canopy micro-sites. Monsoonal rainfall influenced a greater shift in the magnitude of ecosystem CO2 assimilation in the upland shrubland than in the riparian shrubland. Mesquite water status and photosynthetic gas exchange were closely linked to the onset of the North American monsoon in the upland shrubland. In contrast, the presence of shallow alluvial groundwater in the riparian shrubland caused larger size classes of mesquite to be physiologically insensitive to monsoonal rains. In both shrublands, soil respiration was greatest beneath mesquite canopies and was coupled to shallow soil moisture abundance. Physiography, through its constraint on the physiological sensitivity of deeply rooted woody plants, may interact with plant-mediated rates of soil respiration to affect the sensitivity of semiarid-ecosystem carbon exchange in response to episodic rainfall.

A highly stable gadolinium complex with a fast, associative mechanism of water exchange.

PubMed

Thompson, Marlon K; Botta, Mauro; Nicolle, Gaëlle; Helm, Lothar; Aime, Silvio; Merbach, André E; Raymond, Kenneth N

2003-11-26

The stability and water exchange dynamics of gadolinium (GdIII) complexes are critical characteristics that determine their effectiveness as contrast agents for magnetic resonance imaging (MRI). A new heteropodal GdIII chelate, [Gd-TREN-bis(6-Me-HOPO)-(TAM-TRI)(H2O)2] (Gd-2), is presented which is based on a hydroxypyridinate (HOPO)-terephthalamide (TAM) ligand design. Thermodynamic equilibrium constants for the acid-base properties and the GdIII complexation strength of TREN-bis(6-Me-HOPO)-(TAM-TRI) (2) were measured by potentiometric and spectrophotometric titration techniques, respectively. The pGd of 2 is 20.6 (pH 7.4, 25 degrees C, I = 0.1 M), indicating that Gd-2 is of more than sufficient thermodynamic stability for in vivo MRI applications. The water exchange rate of Gd-2 (kex = 5.3(+/-0.6) x 107 s-1) was determined by variable temperature 17O NMR and is in the fast exchange regime - ideal for MRI. Variable pressure 17O NMR was used to determine the volume of activation (DeltaV) of Gd-2. DeltaV for Gd-2 is -5 cm3 mol-1, indicative of an interchange associative (Ia) water exchange mechanism. The results reported herein are important as they provide insight into the factors influencing high stability and fast water exchange in the HOPO series of complexes, potentially future clinical contrast agents.

Dynamic-contrast-enhanced-MRI with extravasating contrast reagent: Rat cerebral glioma blood volume determination

NASA Astrophysics Data System (ADS)

Li, Xin; Rooney, William D.; Várallyay, Csanád G.; Gahramanov, Seymur; Muldoon, Leslie L.; Goodman, James A.; Tagge, Ian J.; Selzer, Audrey H.; Pike, Martin M.; Neuwelt, Edward A.; Springer, Charles S.

2010-10-01

The accurate mapping of the tumor blood volume (TBV) fraction ( vb) is a highly desired imaging biometric goal. It is commonly thought that achieving this is difficult, if not impossible, when small molecule contrast reagents (CRs) are used for the T1-weighted (Dynamic-Contrast-Enhanced) DCE-MRI technique. This is because angiogenic malignant tumor vessels allow facile CR extravasation. Here, a three-site equilibrium water exchange model is applied to DCE-MRI data from the cerebrally-implanted rat brain U87 glioma, a tumor exhibiting rapid CR extravasation. Analyses of segments of the (and the entire) DCE data time-course with this "shutter-speed" pharmacokinetic model, which admits finite water exchange kinetics, allow TBV estimation from the first-pass segment. Pairwise parameter determinances were tested with grid searches of 2D parametric error surfaces. Tumor blood volume ( vb), as well as ve (the extracellular, extravascular space volume fraction), and Ktrans (a CR extravasation rate measure) parametric maps are presented. The role of the Patlak Plot in DCE-MRI is also considered.

Rapid hydraulic recovery in Eucalyptus pauciflora after drought: linkages between stem hydraulics and leaf gas exchange.

PubMed

Martorell, Sebastià; Diaz-Espejo, Antonio; Medrano, Hipólito; Ball, Marilyn C; Choat, Brendan

2014-03-01

In woody plants, photosynthetic capacity is closely linked to rates at which the plant hydraulic system can supply water to the leaf surface. Drought-induced embolism can cause sharp declines in xylem hydraulic conductivity that coincide with stomatal closure and reduced photosynthesis. Recovery of photosynthetic capacity after drought is dependent on restored xylem function, although few data exist to elucidate this coordination. We examined the dynamics of leaf gas exchange and xylem function in Eucalyptus pauciflora seedlings exposed to a cycle of severe water stress and recovery after re-watering. Stomatal closure and leaf turgor loss occurred at water potentials that delayed the extensive spread of embolism through the stem xylem. Stem hydraulic conductance recovered to control levels within 6 h after re-watering despite a severe drought treatment, suggesting an active mechanism embolism repair. However, stomatal conductance did not recover after 10 d of re-watering, effecting tighter control of transpiration post drought. The dynamics of recovery suggest that a combination of hydraulic and non-hydraulic factors influenced stomatal behaviour post drought. © 2013 John Wiley & Sons Ltd.

Monomer–dimer dynamics and distribution of GPI-anchored uPAR are determined by cell surface protein assemblies

PubMed Central

Caiolfa, Valeria R.; Zamai, Moreno; Malengo, Gabriele; Andolfo, Annapaola; Madsen, Chris D.; Sutin, Jason; Digman, Michelle A.; Gratton, Enrico; Blasi, Francesco; Sidenius, Nicolai

2007-01-01

To search for functional links between glycosylphosphatidylinositol (GPI) protein monomer–oligomer exchange and membrane dynamics and confinement, we studied urokinase plasminogen activator (uPA) receptor (uPAR), a GPI receptor involved in the regulation of cell adhesion, migration, and proliferation. Using a functionally active fluorescent protein–uPAR in live cells, we analyzed the effect that extracellular matrix proteins and uPAR ligands have on uPAR dynamics and dimerization at the cell membrane. Vitronectin directs the recruitment of dimers and slows down the diffusion of the receptors at the basal membrane. The commitment to uPA–plasminogen activator inhibitor type 1–mediated endocytosis and recycling modifies uPAR diffusion and induces an exchange between uPAR monomers and dimers. This exchange is fully reversible. The data demonstrate that cell surface protein assemblies are important in regulating the dynamics and localization of uPAR at the cell membrane and the exchange of monomers and dimers. These results also provide a strong rationale for dynamic studies of GPI-anchored molecules in live cells at steady state and in the absence of cross-linker/clustering agents. PMID:18056417

Snow depth manipulation experiments in a dry and a moist tundra

NASA Astrophysics Data System (ADS)

Kwon, M. J.; Czimczik, C. I.; Jung, J. Y.; Kim, M.; Lee, Y. K.; Nam, S.; Wagner, I.

2017-12-01

As a result of global warming, precipitation in the Arctic is expected to increase by 25-50% by the end of this century, mostly in the form of snow. However, precipitation patterns vary considerable in space and time, and future precipitation patterns are highly uncertain at local and regional scales. The amount of snowfall (or snow depth) influences a number of ecosystem properties in Arctic ecosystems, such as soil temperature over winter and soil moisture in the following growing season. These modifications then affect rates of carbon-related soil processes and photosynthesis, thus CO2 exchange rates between terrestrial ecosystems and the atmosphere. In this study, we investigate the effects of snow depth on the magnitude, sources and temporal dynamics of CO2 fluxes. We installed snow fences in a dry dwarf-shrub (Cambridge Bay, Canada; 69° N, 105° W) and a moist low-shrub (Council, Alaska, USA; 64° N, 165° W) tundra in summer 2017, and established control, and increased and reduced snow depth plots at each snow fence. Summertime CO2 flux rates (net ecosystem exchange, ecosystem respiration, gross primary production) and the fractions of autotrophic and heterotrophic respiration to ecosystem respiration were measured using manual chambers and radiocarbon signatures. Wintertime CO2 flux rates will be measured using soda lime adsorption technique and forced diffusion chambers. Soil temperature and moisture at multiple depths, as well as changes in soil properties and microbial communities will be also observed, to research whether these changes affect CO2 flux rates or patterns. Our study will elucidate how future snow depth and its impact on soil physical and biogeochemical properties influence the magnitude and sources of tundra-atmosphere CO2 exchange in the rapidly warming Arctic.

The New S-RAM Air Variable Compressor/Expander for Heat Pump and Waste Heat to Power Application

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

Dehoff, Ryan R; Jestings, Lee; Conde, Ricardo

S-RAM Dynamics (S-RAM) has designed an innovative heat pump system targeted for commercial and industrial applications. This new heat pump system is more efficient than anything currently on the market and utilizes air as the refrigerant instead of hydrofluorocarbon (HFC) refrigerants, leading to lower operating costs, minimal environmental costs or concerns, and lower maintenance costs. The heat pumps will be manufactured in the United States. This project was aimed at determining the feasibility of utilizing additive manufacturing to make the heat exchanger device for the new heat pump system. ORNL and S-RAM Dynamics collaborated on determining the prototype performance andmore » subsequently printing of the prototype using additive manufacturing. Complex heat exchanger designs were fabricated using the Arcam electron beam melting (EBM) powder bed technology using Ti-6Al-4V material. An ultrasonic welding system was utilized in order to remove the powder from the small openings of the heat exchanger. The majority of powder in the small chambers was removed, however, the amount of powder remaining in the heat exchanger was a function of geometry. Therefore, only certain geometries of heat exchangers could be fabricated. SRAM Dynamics evaluated a preliminary heat exchanger design. Although the results of the additive manufacturing of the heat exchanger were not optimum, a less complex geometry was demonstrated. A sleeve valve was used as a demonstration piece, as engine designs from S-RAM Dynamics require the engine to have a very high density. Preliminary designs of this geometry were successfully fabricated using the EBM technology.« less

Assessing the Efficacy of Adjustable Moving Averages Using ASEAN-5 Currencies.

PubMed

Chan Phooi M'ng, Jacinta; Zainudin, Rozaimah

2016-01-01

The objective of this research is to examine the trends in the exchange rate markets of the ASEAN-5 countries (Indonesia (IDR), Malaysia (MYR), the Philippines (PHP), Singapore (SGD), and Thailand (THB)) through the application of dynamic moving average trading systems. This research offers evidence of the usefulness of the time-varying volatility technical analysis indicator, Adjustable Moving Average (AMA') in deciphering trends in these ASEAN-5 exchange rate markets. This time-varying volatility factor, referred to as the Efficacy Ratio in this paper, is embedded in AMA'. The Efficacy Ratio adjusts the AMA' to the prevailing market conditions by avoiding whipsaws (losses due, in part, to acting on wrong trading signals, which generally occur when there is no general direction in the market) in range trading and by entering early into new trends in trend trading. The efficacy of AMA' is assessed against other popular moving-average rules. Based on the January 2005 to December 2014 dataset, our findings show that the moving averages and AMA' are superior to the passive buy-and-hold strategy. Specifically, AMA' outperforms the other models for the United States Dollar against PHP (USD/PHP) and USD/THB currency pairs. The results show that different length moving averages perform better in different periods for the five currencies. This is consistent with our hypothesis that a dynamic adjustable technical indicator is needed to cater for different periods in different markets.

Water permeability of spider dragline silk.

PubMed

Li, Xiang; Eles, Philip T; Michal, Carl A

2009-05-11

The water permeability of spider dragline silk was studied by measuring changes in amide deuteration of D(2)O-soaked silk with solid-state NMR. (13)C-D rotational-echo double-resonance (REDOR) NMR experiments showed that chemical exchange of amide hydrogen occurs in a large fraction of amino acids, including over 50% of alanine residues, which are known to exist predominantly in beta-sheet crystallites. This suggests that a substantial fraction of the crystalline regions are permeable to water, at least on the time scale of hours, implying that they are more dynamic, and therefore susceptible to chemical exchange with water, than previously thought. Wideline deuterium NMR spectra of dried D(2)O-soaked silk showed a combination of quadrupolar broadened and motionally averaged isotropic components whose intensities change on the time scale of hours. These results are interpreted in terms of chemical exchange between deuterium on the protein backbone, residual water within the silk, and water vapor in the ambient atmosphere. A simple compartmental model fits the results well and yields rate constants for the exchange processes. The model requires the inclusion of a compartment that does not undergo exchange. This compartment, likely related to the crystalline region, is interesting because it is accessible to water in wet silk, but impervious to any remaining free water when the silk is dried.

All-atom molecular dynamics calculation study of entire poliovirus empty capsids in solution

NASA Astrophysics Data System (ADS)

Andoh, Y.; Yoshii, N.; Yamada, A.; Fujimoto, K.; Kojima, H.; Mizutani, K.; Nakagawa, A.; Nomoto, A.; Okazaki, S.

2014-10-01

Small viruses that belong, for example, to the Picornaviridae, such as poliovirus and foot-and-mouth disease virus, consist simply of capsid proteins and a single-stranded RNA (ssRNA) genome. The capsids are quite stable in solution to protect the genome from the environment. Here, based on long-time and large-scale 6.5 × 106 all-atom molecular dynamics calculations for the Mahoney strain of poliovirus, we show microscopic properties of the viral capsids at a molecular level. First, we found equilibrium rapid exchange of water molecules across the capsid. The exchange rate is so high that all water molecules inside the capsid (about 200 000) can leave the capsid and be replaced by water molecules from the outside in about 25 μs. This explains the capsid's tolerance to high pressures and deactivation by exsiccation. In contrast, the capsid did not exchange ions, at least within the present simulation time of 200 ns. This implies that the capsid can function, in principle, as a semipermeable membrane. We also found that, similar to the xylem of trees, the pressure of the solution inside the capsid without the genome was negative. This is caused by coulombic interaction of the solution inside the capsid with the capsid excess charges. The negative pressure may be compensated by positive osmotic pressure by the solution-soluble ssRNA and the counter ions introduced into it.

Effects of exchange rate volatility on export volume and prices of forest products

Treesearch

Sijia Zhang; Joseph Buongiorno

2010-01-01

The relative value of currencies varies considerably over time. These fluctuations bring uncertainty to international traders. As a result, the volatility in exchange rate movements may influence the volume and the price of traded commodities. The volatility of exchange rates was measured by the variance of residuals in a GARCH(1,1) model of the exchange rate. We...

International finance, Lévy distributions, and the econophysics of exchange rates

NASA Astrophysics Data System (ADS)

Da Silva, Sergio; Matsushita, Raul; Gleria, Iram; Figueiredo, Annibal; Rathie, Pushpa

2005-06-01

This paper surveys the developments in the field of international finance, in particular the research of economists on foreign exchange rates. That might be of interest to physicists working on the econophysics of exchange rates. We show how the econophysics agenda might follow naturally from the economists' research. We also present our own work on the econophysics of exchange rates.

Drought response strategies define the relative contributions of hydraulic dysfunction and carbohydrate depletion during tree mortality.

PubMed

Mitchell, Patrick J; O'Grady, Anthony P; Tissue, David T; White, Donald A; Ottenschlaeger, Maria L; Pinkard, Elizabeth A

2013-02-01

Plant survival during drought requires adequate hydration in living tissues and carbohydrate reserves for maintenance and recovery. We hypothesized that tree growth and hydraulic strategy determines the intensity and duration of the 'physiological drought', thereby affecting the relative contributions of loss of hydraulic function and carbohydrate depletion during mortality. We compared patterns in growth rate, water relations, gas exchange and carbohydrate dynamics in three tree species subjected to prolonged drought. Two Eucalyptus species (E. globulus, E. smithii) exhibited high growth rates and water-use resulting in rapid declines in water status and hydraulic conductance. In contrast, conservative growth and water relations in Pinus radiata resulted in longer periods of negative carbon balance and significant depletion of stored carbohydrates in all organs. The ongoing demand for carbohydrates from sustained respiration highlighted the role that duration of drought plays in facilitating carbohydrate consumption. Two drought strategies were revealed, differentiated by plant regulation of water status: plants maximized gas exchange, but were exposed to low water potentials and rapid hydraulic dysfunction; and tight regulation of gas exchange at the cost of carbohydrate depletion. These findings provide evidence for a relationship between hydraulic regulation of water status and carbohydrate depletion during terminal drought. © 2012 CSIRO. New Phytologist © 2012 New Phytologist Trust.

12 CFR Appendix A to Subpart A of... - Minimum Capital Components for Interest Rate and Foreign Exchange Rate Contracts

Code of Federal Regulations, 2010 CFR

2010-01-01

... sheet interest rate and foreign exchange rate contracts: a. Interest Rate Contracts i. Single currency... Contracts i. Cross-currency interest rate swaps. ii. Forward foreign exchange rate contracts. iii. Currency... exposure is zero. Mark-to-market values are measured in United States dollars, regardless of the currency...

Ozone uptake, water loss and carbon exchange dynamics in annually drought-stressed Pinus ponderosa forests: measured trends and parameters for uptake modeling.

PubMed

Panek, Jeanne A

2004-03-01

This paper describes 3 years of physiological measurements on ponderosa pine (Pinus ponderosa Dougl. ex Laws.) growing along an ozone concentration gradient in the Sierra Nevada, California, including variables necessary to parameterize, validate and modify photosynthesis and stomatal conductance algorithms used to estimate ozone uptake. At all sites, gas exchange was under tight stomatal control during the growing season. Stomatal conductance was strongly correlated with leaf water potential (R2=0.82), which decreased over the growing season with decreasing soil water content (R2=0.60). Ozone uptake, carbon uptake, and transpirational water loss closely followed the dynamics of stomatal conductance. Peak ozone and CO2 uptake occurred in early summer and declined progressively thereafter. As a result, periods of maximum ozone uptake did not correspond to periods of peak ozone concentration, underscoring the inappropriateness of using current metrics based on concentration (e.g., SUM0, W126 and AOT40) for assessing ozone exposure risk to plants in this climate region. Both Jmax (maximum CO2-saturated photosynthetic rate, limited by electron transport) and Vcmax (maximum rate of Rubisco-limited carboxylation) increased toward the middle of the growing season, then decreased in September. Intrinsic water-use efficiency rose with increasing drought stress, as expected. The ratio of Jmax to Vcmax was similar to literature values of 2.0. Nighttime respiration followed a Q10 of 2.0, but was significantly higher at the high-ozone site. Respiration rates decreased by the end of the summer as a result of decreased metabolic activity and carbon stores.

Proper interpretation of dissolved nitrous oxide isotopes, production pathways, and emissions requires a modelling approach.

PubMed

Thuss, Simon J; Venkiteswaran, Jason J; Schiff, Sherry L

2014-01-01

Stable isotopes ([Formula: see text]15N and [Formula: see text]18O) of the greenhouse gas N2O provide information about the sources and processes leading to N2O production and emission from aquatic ecosystems to the atmosphere. In turn, this describes the fate of nitrogen in the aquatic environment since N2O is an obligate intermediate of denitrification and can be a by-product of nitrification. However, due to exchange with the atmosphere, the [Formula: see text] values at typical concentrations in aquatic ecosystems differ significantly from both the source of N2O and the N2O emitted to the atmosphere. A dynamic model, SIDNO, was developed to explore the relationship between the isotopic ratios of N2O, N2O source, and the emitted N2O. If the N2O production rate or isotopic ratios vary, then the N2O concentration and isotopic ratios may vary or be constant, not necessarily concomitantly, depending on the synchronicity of production rate and source isotopic ratios. Thus prima facie interpretation of patterns in dissolved N2O concentrations and isotopic ratios is difficult. The dynamic model may be used to correctly interpret diel field data and allows for the estimation of the gas exchange coefficient, N2O production rate, and the production-weighted [Formula: see text] values of the N2O source in aquatic ecosystems. Combining field data with these modelling efforts allows this critical piece of nitrogen cycling and N2O flux to the atmosphere to be assessed.

Deposition rates of fungal spores in indoor environments, factors effecting them and comparison with non-biological aerosols

NASA Astrophysics Data System (ADS)

Kanaani, Hussein; Hargreaves, Megan; Ristovski, Zoran; Morawska, Lidia

Particle deposition indoors is one of the most important factors that determine the effect of particle exposure on human health. While many studies have investigated the particle deposition of non-biological aerosols, few have investigated biological aerosols and even fewer have studied fungal spore deposition indoors. The purpose of this study was, for the first time, to investigate the deposition rates of fungal particles in a chamber of 20.4 m 3 simulating indoor environments by: (1) releasing fungal particles into the chamber, in sufficient concentrations so the particle deposition rates can be statistically analysed; (2) comparing the obtained deposition rates with non-bioaerosol particles of similar sizes, investigated under the same conditions; and (3) investigating the effects of ventilation on the particle deposition rates. The study was conducted for a wide size range of particle sizes (0.54-6.24 μm), at three different air exchange rates (0.009, 1.75 and 2.5 h -1). An Ultraviolet Aerodynamic Particle Sizer Spectrometer (UVAPS) was used to monitor the particle concentration decay rate. The study showed that the deposition rates of fungal spores ( Aspergillus niger and Penicillium species) and the other aerosols (canola oil and talcum powder) were similar, especially at very low air exchange rates (in the order of 0.009). Both the aerosol and the bioaerosol deposition rates were found to be a function of particle size. The results also showed increasing deposition rates with increasing ventilation rates, for all particles under investigation. These conclusions are important in understanding the dynamics of fungal spores in the air.

Particle Models with Self Sustained Current

NASA Astrophysics Data System (ADS)

Colangeli, M.; De Masi, A.; Presutti, E.

2017-06-01

We present some computer simulations run on a stochastic cellular automaton (CA). The CA simulates a gas of particles which are in a channel,the interval [1, L] in Z, but also in "reservoirs" R_1 and R_2. The evolution in the channel simulates a lattice gas with Kawasaki dynamics with attractive Kac interactions; the temperature is chosen smaller than the mean field critical one. There are also exchanges of particles between the channel and the reservoirs and among reservoirs. When the rate of exchanges among reservoirs is in a suitable interval the CA reaches an apparently stationary state with a non zero current; for different choices of the initial condition the current changes sign. We have a quite satisfactory theory of the phenomenon but we miss a full mathematical proof.

Temperature dependence of chloride, bromide, iodide, thiocyanate and salicylate transport in human red cells

PubMed Central

Dalmark, Mads; Wieth, Jens Otto

1972-01-01

1. The temperature dependence of the steady-state self-exchange of chloride between human red cells and a plasma-like electrolyte medium has been studied by measuring the rate of 36Cl- efflux from radioactively labelled cells. Between 0 and 10° C the rate increased by a factor of eight corresponding to an Arrhenius activation energy of 33 kcal/mole. 2. The rate of chloride exchange decreased significantly in experiments where 95% of the chloride ions in cells and medium were replaced by other monovalent anions of a lyotropic series. The rate of chloride self-exchange was increasingly reduced by bromide, bicarbonate, nitrate, iodide, thiocyanate, and salicylate. The latter aromatic anion was by far the most potent inhibitor, reducing the rate of chloride self-exchange to 0·2% of the value found in a chloride medium. 3. The temperature sensitivity of the chloride self-exchange was not affected significantly by the anionic inhibitors. The Arrhenius activation energies of chloride exchange were between 30 and 40 kcal/mole in the presence of the six inhibitory anions mentioned above. 4. The rate of self-exchange of bromide, thiocyanate, and iodide between human red cells and media was determined after washing and labelling cells in media containing 120 mM bromide, thiocyanate, or iodide respectively. The rate of self-exchange of the three anions were 12, 3, and 0·4% of the rate of chloride self-exchange found in the chloride medium. 5. The Arrhenius activation energies of the self-exchange of bromide, iodide, and thiocyanate were all between 29 and 37 kcal/mole, the same magnitude as found for the self-exchange of chloride. 6. Although approximately 40% of the intracellular iodide and salicylate ions appeared to be adsorbed to intracellular proteins, the rate of tracer anion efflux followed first order kinetics until at least 98% of the intracellular anions had been exchanged. 7. The self-exchange of salicylate across the human red cell membrane occurred by a different mechanism than the one utilized by the inorganic monovalent anions. The activation energy of salicylate exchange (13·2 kcal/mole) was significantly lower than that of inorganic anion exchange. Salicylate exchange increased with decreasing pH in contrast to the exchange of chloride, which decreases when pH is lowered. PMID:5071931

Control of the Ability of Profilin to Bind and Facilitate Nucleotide Exchange from G-actin*

PubMed Central

Wen, Kuo-Kuang; McKane, Melissa; Houtman, Jon C. D.; Rubenstein, Peter A.

2008-01-01

A major factor in profilin regulation of actin cytoskeletal dynamics is its facilitation of G-actin nucleotide exchange. However, the mechanism of this facilitation is unknown. We studied the interaction of yeast (YPF) and human profilin 1 (HPF1) with yeast and mammalian skeletal muscle actins. Homologous pairs (YPF and yeast actin, HPF1 and muscle actin) bound more tightly to one another than heterologous pairs. However, with saturating profilin, HPF1 caused a faster etheno-ATP exchange with both yeast and muscle actins than did YPF. Based on the -fold change in ATP exchange rate/Kd, however, the homologous pairs are more efficient than the heterologous pairs. Thus, strength of binding of profilin to actin and nucleotide exchange rate are not tightly coupled. Actin/HPF interactions were entropically driven, whereas YPF interactions were enthalpically driven. Hybrid yeast actins containing subdomain 1 (sub1) or subdomain 1 and 2 (sub12) muscle actin residues bound more weakly to YPF than did yeast actin (Kd = 2 μm versus 0.6 μm). These hybrids bound even more weakly to HPF than did yeast actin (Kd = 5 μm versus 3.2 μm). sub1/YPF interactions were entropically driven, whereas the sub12/YPF binding was enthalpically driven. Compared with WT yeast actin, YPF binding to sub1 occurred with a 5 times faster koff and a 2 times faster kon. sub12 bound with a 3 times faster koff and a 1.5 times slower kon. Profilin controls the energetics of its interaction with nonhybrid actin, but interactions between actin subdomains 1 and 2 affect the topography of the profilin binding site. PMID:18223293

Evaluation of Enhanced Sampling Provided by Accelerated Molecular Dynamics with Hamiltonian Replica Exchange Methods

PubMed Central

2015-01-01

Many problems studied via molecular dynamics require accurate estimates of various thermodynamic properties, such as the free energies of different states of a system, which in turn requires well-converged sampling of the ensemble of possible structures. Enhanced sampling techniques are often applied to provide faster convergence than is possible with traditional molecular dynamics simulations. Hamiltonian replica exchange molecular dynamics (H-REMD) is a particularly attractive method, as it allows the incorporation of a variety of enhanced sampling techniques through modifications to the various Hamiltonians. In this work, we study the enhanced sampling of the RNA tetranucleotide r(GACC) provided by H-REMD combined with accelerated molecular dynamics (aMD), where a boosting potential is applied to torsions, and compare this to the enhanced sampling provided by H-REMD in which torsion potential barrier heights are scaled down to lower force constants. We show that H-REMD and multidimensional REMD (M-REMD) combined with aMD does indeed enhance sampling for r(GACC), and that the addition of the temperature dimension in the M-REMD simulations is necessary to efficiently sample rare conformations. Interestingly, we find that the rate of convergence can be improved in a single H-REMD dimension by simply increasing the number of replicas from 8 to 24 without increasing the maximum level of bias. The results also indicate that factors beyond replica spacing, such as round trip times and time spent at each replica, must be considered in order to achieve optimal sampling efficiency. PMID:24625009

Riparian hydraulic gradient and stream-groundwater exchange dynamics in steep headwater valleys

Treesearch

T.J. Voltz; M.N. Gooseff; A.S. Ward; K. Singha; M. Fitzgerald; T. Wagener

2013-01-01

Patterns of riparian hydraulic gradients and stream-groundwater exchange in headwater catchments provide the hydrologic context for important ecological processes. Although the controls are relatively well understood, their dynamics during periods of hydrologic change is not. We investigate riparian hydraulic gradients over three different time scales in two steep,...

Infrared thermography of evaporative fluxes and dynamics of salt deposition on heterogeneous porous surfaces

NASA Astrophysics Data System (ADS)

Nachshon, Uri; Shahraeeni, Ebrahim; Or, Dani; Dragila, Maria; Weisbrod, Noam

2011-12-01

Evaporation of saline solutions from porous media, common in arid areas, involves complex interactions between mass transport, energy exchange and phase transitions. We quantified evaporation of saline solutions from heterogeneous sand columns under constant hydraulic boundary conditions to focus on effects of salt precipitation on evaporation dynamics. Mass loss measurements and infrared thermography were used to quantify evaporation rates. The latter method enables quantification of spatial and temporal variability of salt precipitation to identify its dynamic effects on evaporation. Evaporation from columns filled with texturally-contrasting sand using different salt solutions revealed preferential salt precipitation within the fine textured domains. Salt precipitation reduced evaporation rates from the fine textured regions by nearly an order of magnitude. In contrast, low evaporation rates from coarse-textured regions (due to low capillary drive) exhibited less salt precipitation and consequently less evaporation rate suppression. Experiments provided insights into two new phenomena: (1) a distinct increase in evaporation rate at the onset of evaporation; and (2) a vapor pumping mechanism related to the presence of a salt crust over semidry media. Both phenomena are related to local vapor pressure gradients established between pore water and the surface salt crust. Comparison of two salts: NaCl and NaI, which tend to precipitate above the matrix surface and within matrix pores, respectively, shows a much stronger influence of NaCl on evaporation rate suppression. This disparity reflects the limited effect of NaI precipitation on matrix resistivity for solution and vapor flows.

Equilibrious Strand Exchange Promoted by DNA Conformational Switching

NASA Astrophysics Data System (ADS)

Wu, Zhiguo; Xie, Xiao; Li, Puzhen; Zhao, Jiayi; Huang, Lili; Zhou, Xiang

2013-01-01

Most of DNA strand exchange reactions in vitro are based on toehold strategy which is generally nonequilibrium, and intracellular strand exchange mediated by proteins shows little sequence specificity. Herein, a new strand exchange promoted by equilibrious DNA conformational switching is verified. Duplexes containing c-myc sequence which is potentially converted into G-quadruplex are designed in this strategy. The dynamic equilibrium between duplex and G4-DNA is response to the specific exchange of homologous single-stranded DNA (ssDNA). The SER is enzyme free and sequence specific. No ATP is needed and the displaced ssDNAs are identical to the homologous ssDNAs. The SER products and exchange kenetics are analyzed by PAGE and the RecA mediated SER is performed as the contrast. This SER is a new feature of G4-DNAs and a novel strategy to utilize the dynamic equilibrium of DNA conformations.

Functional Dynamics of Hexameric Helicase Probed by Hydrogen Exchange and Simulation

PubMed Central

Radou, Gaël; Dreyer, Frauke N.; Tuma, Roman; Paci, Emanuele

2014-01-01

The biological function of large macromolecular assemblies depends on their structure and their dynamics over a broad range of timescales; for this reason, it is a significant challenge to investigate these assemblies using conventional experimental techniques. One of the most promising experimental techniques is hydrogen-deuterium exchange detected by mass spectrometry. Here, we describe to our knowledge a new computational method for quantitative interpretation of deuterium exchange kinetics and apply it to a hexameric viral helicase P4 that unwinds and translocates RNA into a virus capsid at the expense of ATP hydrolysis. Room-temperature dynamics probed by a hundred nanoseconds of all-atom molecular dynamics simulations is sufficient to predict the exchange kinetics of most sequence fragments and provide a residue-level interpretation of the low-resolution experimental results. The strategy presented here is also a valuable tool to validate experimental data, e.g., assignments, and to probe mechanisms that cannot be observed by x-ray crystallography, or that occur over timescales longer than those that can be realistically simulated, such as the opening of the hexameric ring. PMID:25140434

Structural Dynamics Control Allosteric Activation of Cytohesin Family Arf GTPase Exchange Factors

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

Malaby, Andrew W.; Das, Sanchaita; Chakravarthy, Srinivas

Membrane dynamic processes including vesicle biogenesis depend on Arf guanosine triphosphatase (GTPase) activation by guanine nucleotide exchange factors (GEFs) containing a catalytic Sec7 domain and a membrane-targeting module such as a pleckstrin homology (PH) domain. The catalytic output of cytohesin family Arf GEFs is controlled by autoinhibitory interactions that impede accessibility of the exchange site in the Sec7 domain. These restraints can be relieved through activator Arf-GTP binding to an allosteric site comprising the PH domain and proximal autoinhibitory elements (Sec7-PH linker and C-terminal helix). Small-angle X-ray scattering and negative-stain electron microscopy were used to investigate the structural organization andmore » conformational dynamics of cytohesin-3 (Grp1) in autoinhibited and active states. The results support a model in which hinge dynamics in the autoinhibited state expose the activator site for Arf-GTP binding, while subsequent C-terminal helix unlatching and repositioning unleash conformational entropy in the Sec7-PH linker to drive exposure of the exchange site.« less

Ozone and limonene in indoor air: a source of submicron particle exposure.

PubMed Central

Wainman, T; Zhang, J; Weschler, C J; Lioy, P J

2000-01-01

Little information currently exists regarding the occurrence of secondary organic aerosol formation in indoor air. Smog chamber studies have demonstrated that high aerosol yields result from the reaction of ozone with terpenes, both of which commonly occur in indoor air. However, smog chambers are typically static systems, whereas indoor environments are dynamic. We conducted a series of experiments to investigate the potential for secondary aerosol in indoor air as a result of the reaction of ozone with d-limonene, a compound commonly used in air fresheners. A dynamic chamber design was used in which a smaller chamber was nested inside a larger one, with air exchange occurring between the two. The inner chamber was used to represent a model indoor environment and was operated at an air exchange rate below 1 exchange/hr, while the outer chamber was operated at a high air exchange rate of approximately 45 exchanges/hr. Limonene was introduced into the inner chamber either by the evaporation of reagent-grade d-limonene or by inserting a lemon-scented, solid air freshener. A series of ozone injections were made into the inner chamber during the course of each experiment, and an optical particle counter was used to measure the particle concentration. Measurable particle formation and growth occurred almost exclusively in the 0.1-0.2 microm and 0.2-0.3 microm size fractions in all of the experiments. Particle formation in the 0.1-0.2 microm size range occurred as soon as ozone was introduced, but the formation of particles in the 0.2-0.3 microm size range did not occur until at least the second ozone injection occurred. The results of this study show a clear potential for significant particle concentrations to be produced in indoor environments as a result of secondary particle formation via the ozone-limonene reaction. Because people spend the majority of their time indoors, secondary particles formed in indoor environments may make a significant contribution to overall particle exposure. This study provides data for assessing the impact of outdoor ozone on indoor particles. This is important to determine the efficacy of the mass-based particulate matter standards in protecting public health because the indoor secondary particles can vary coincidently with the variations of outdoor fine particles in summer. PMID:11133393

Ozone and limonene in indoor air: a source of submicron particle exposure.

PubMed

Wainman, T; Zhang, J; Weschler, C J; Lioy, P J

2000-12-01

Little information currently exists regarding the occurrence of secondary organic aerosol formation in indoor air. Smog chamber studies have demonstrated that high aerosol yields result from the reaction of ozone with terpenes, both of which commonly occur in indoor air. However, smog chambers are typically static systems, whereas indoor environments are dynamic. We conducted a series of experiments to investigate the potential for secondary aerosol in indoor air as a result of the reaction of ozone with d-limonene, a compound commonly used in air fresheners. A dynamic chamber design was used in which a smaller chamber was nested inside a larger one, with air exchange occurring between the two. The inner chamber was used to represent a model indoor environment and was operated at an air exchange rate below 1 exchange/hr, while the outer chamber was operated at a high air exchange rate of approximately 45 exchanges/hr. Limonene was introduced into the inner chamber either by the evaporation of reagent-grade d-limonene or by inserting a lemon-scented, solid air freshener. A series of ozone injections were made into the inner chamber during the course of each experiment, and an optical particle counter was used to measure the particle concentration. Measurable particle formation and growth occurred almost exclusively in the 0.1-0.2 microm and 0.2-0.3 microm size fractions in all of the experiments. Particle formation in the 0.1-0.2 microm size range occurred as soon as ozone was introduced, but the formation of particles in the 0.2-0.3 microm size range did not occur until at least the second ozone injection occurred. The results of this study show a clear potential for significant particle concentrations to be produced in indoor environments as a result of secondary particle formation via the ozone-limonene reaction. Because people spend the majority of their time indoors, secondary particles formed in indoor environments may make a significant contribution to overall particle exposure. This study provides data for assessing the impact of outdoor ozone on indoor particles. This is important to determine the efficacy of the mass-based particulate matter standards in protecting public health because the indoor secondary particles can vary coincidently with the variations of outdoor fine particles in summer.

An integrated model of cardiac mitochondrial energy metabolism and calcium dynamics.

PubMed

Cortassa, Sonia; Aon, Miguel A; Marbán, Eduardo; Winslow, Raimond L; O'Rourke, Brian

2003-04-01

We present an integrated thermokinetic model describing control of cardiac mitochondrial bioenergetics. The model describes the tricarboxylic acid (TCA) cycle, oxidative phosphorylation, and mitochondrial Ca(2+) handling. The kinetic component of the model includes effectors of the TCA cycle enzymes regulating production of NADH and FADH(2), which in turn are used by the electron transport chain to establish a proton motive force (Delta mu(H)), driving the F(1)F(0)-ATPase. In addition, mitochondrial matrix Ca(2+), determined by Ca(2+) uniporter and Na(+)/Ca(2+) exchanger activities, regulates activity of the TCA cycle enzymes isocitrate dehydrogenase and alpha-ketoglutarate dehydrogenase. The model is described by twelve ordinary differential equations for the time rate of change of mitochondrial membrane potential (Delta Psi(m)), and matrix concentrations of Ca(2+), NADH, ADP, and TCA cycle intermediates. The model is used to predict the response of mitochondria to changes in substrate delivery, metabolic inhibition, the rate of adenine nucleotide exchange, and Ca(2+). The model is able to reproduce, qualitatively and semiquantitatively, experimental data concerning mitochondrial bioenergetics, Ca(2+) dynamics, and respiratory control. Significant increases in oxygen consumption (V(O(2))), proton efflux, NADH, and ATP synthesis, in response to an increase in cytoplasmic Ca(2+), are obtained when the Ca(2+)-sensitive dehydrogenases are the main rate-controlling steps of respiratory flux. These responses diminished when control is shifted downstream (e.g., the respiratory chain or adenine nucleotide translocator). The time-dependent behavior of the model, under conditions simulating an increase in workload, closely reproduces experimentally observed mitochondrial NADH dynamics in heart trabeculae subjected to changes in pacing frequency. The steady-state and time-dependent behavior of the model support the hypothesis that mitochondrial matrix Ca(2+) plays an important role in matching energy supply with demand in cardiac myocytes.

An Integrated Model of Cardiac Mitochondrial Energy Metabolism and Calcium Dynamics

PubMed Central

Cortassa, Sonia; Aon, Miguel A.; Marbán, Eduardo; Winslow, Raimond L.; O'Rourke, Brian

2003-01-01

We present an integrated thermokinetic model describing control of cardiac mitochondrial bioenergetics. The model describes the tricarboxylic acid (TCA) cycle, oxidative phosphorylation, and mitochondrial Ca2+ handling. The kinetic component of the model includes effectors of the TCA cycle enzymes regulating production of NADH and FADH2, which in turn are used by the electron transport chain to establish a proton motive force (ΔμH), driving the F1F0-ATPase. In addition, mitochondrial matrix Ca2+, determined by Ca2+ uniporter and Na+/Ca2+ exchanger activities, regulates activity of the TCA cycle enzymes isocitrate dehydrogenase and α-ketoglutarate dehydrogenase. The model is described by twelve ordinary differential equations for the time rate of change of mitochondrial membrane potential (ΔΨm), and matrix concentrations of Ca2+, NADH, ADP, and TCA cycle intermediates. The model is used to predict the response of mitochondria to changes in substrate delivery, metabolic inhibition, the rate of adenine nucleotide exchange, and Ca2+. The model is able to reproduce, qualitatively and semiquantitatively, experimental data concerning mitochondrial bioenergetics, Ca2+ dynamics, and respiratory control. Significant increases in oxygen consumption (VO2), proton efflux, NADH, and ATP synthesis, in response to an increase in cytoplasmic Ca2+, are obtained when the Ca2+-sensitive dehydrogenases are the main rate-controlling steps of respiratory flux. These responses diminished when control is shifted downstream (e.g., the respiratory chain or adenine nucleotide translocator). The time-dependent behavior of the model, under conditions simulating an increase in workload, closely reproduces experimentally observed mitochondrial NADH dynamics in heart trabeculae subjected to changes in pacing frequency. The steady-state and time-dependent behavior of the model support the hypothesis that mitochondrial matrix Ca2+ plays an important role in matching energy supply with demand in cardiac myocytes. PMID:12668482

Upgrading a high-throughput spectrometer for high-frequency (<400 kHz) measurements

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

Nishizawa, T., E-mail: nishizawa@wisc.edu; Nornberg, M. D.; Den Hartog, D. J.

2016-11-15

The upgraded spectrometer used for charge exchange recombination spectroscopy on the Madison Symmetric Torus resolves emission fluctuations up to 400 kHz. The transimpedance amplifier’s cutoff frequency was increased based upon simulations comparing the change in the measured photon counts for time-dynamic signals. We modeled each signal-processing stage of the diagnostic and scanned the filtering frequency to quantify the uncertainty in the photon counting rate. This modeling showed that uncertainties can be calculated based on assuming each amplification stage is a Poisson process and by calibrating the photon counting rate with a DC light source to address additional variation.

Upgrading a high-throughput spectrometer for high-frequency (<400 kHz) measurements

NASA Astrophysics Data System (ADS)

Nishizawa, T.; Nornberg, M. D.; Den Hartog, D. J.; Craig, D.

2016-11-01

The upgraded spectrometer used for charge exchange recombination spectroscopy on the Madison Symmetric Torus resolves emission fluctuations up to 400 kHz. The transimpedance amplifier's cutoff frequency was increased based upon simulations comparing the change in the measured photon counts for time-dynamic signals. We modeled each signal-processing stage of the diagnostic and scanned the filtering frequency to quantify the uncertainty in the photon counting rate. This modeling showed that uncertainties can be calculated based on assuming each amplification stage is a Poisson process and by calibrating the photon counting rate with a DC light source to address additional variation.

Markov model of the loan portfolio dynamics considering influence of management and external economic factors

NASA Astrophysics Data System (ADS)

Bozhalkina, Yana; Timofeeva, Galina

2016-12-01

Mathematical model of loan portfolio in the form of a controlled Markov chain with discrete time is considered. It is assumed that coefficients of migration matrix depend on corrective actions and external factors. Corrective actions include process of receiving applications, interaction with existing solvent and insolvent clients. External factors are macroeconomic indicators, such as inflation and unemployment rates, exchange rates, consumer price indices, etc. Changes in corrective actions adjust the intensity of transitions in the migration matrix. The mathematical model for forecasting the credit portfolio structure taking into account a cumulative impact of internal and external changes is obtained.

An ultrastable conjugate of silver nanoparticles and protein formed through weak interactions

NASA Astrophysics Data System (ADS)

Brahmkhatri, Varsha P.; Chandra, Kousik; Dubey, Abhinav; Atreya, Hanudatta S.

2015-07-01

In recent years, silver nanoparticles (AgNPs) have attracted significant attention owing to their unique physicochemical, optical, conductive and antimicrobial properties. One of the properties of AgNPs which is crucial for all applications is their stability. In the present study we unravel a mechanism through which silver nanoparticles are rendered ultrastable in an aqueous solution in complex with the protein ubiquitin (Ubq). This involves a dynamic and reversible association and dissociation of ubiquitin from the surface of AgNP. The exchange occurs at a rate much greater than 25 s-1 implying a residence time of <40 ms for the protein. The AgNP-Ubq complex remains stable for months due to steric stabilization over a wide pH range compared to unconjugated AgNPs. NMR studies reveal that the protein molecules bind reversibly to AgNP with an approximate dissociation constant of 55 μM and undergo fast exchange. At pH > 4 the positively charged surface of the protein comes in contact with the citrate capped AgNP surface. Further, NMR relaxation-based experiments suggest that in addition to the dynamic exchange, a conformational rearrangement of the protein takes place upon binding to AgNP. The ultrastability of the AgNP-Ubq complex was found to be useful for its anti-microbial activity, which allowed the recycling of this complex multiple times without the loss of stability. Altogether, the study provides new insights into the mechanism of protein-silver nanoparticle interactions and opens up new avenues for its application in a wide range of systems.In recent years, silver nanoparticles (AgNPs) have attracted significant attention owing to their unique physicochemical, optical, conductive and antimicrobial properties. One of the properties of AgNPs which is crucial for all applications is their stability. In the present study we unravel a mechanism through which silver nanoparticles are rendered ultrastable in an aqueous solution in complex with the protein ubiquitin (Ubq). This involves a dynamic and reversible association and dissociation of ubiquitin from the surface of AgNP. The exchange occurs at a rate much greater than 25 s-1 implying a residence time of <40 ms for the protein. The AgNP-Ubq complex remains stable for months due to steric stabilization over a wide pH range compared to unconjugated AgNPs. NMR studies reveal that the protein molecules bind reversibly to AgNP with an approximate dissociation constant of 55 μM and undergo fast exchange. At pH > 4 the positively charged surface of the protein comes in contact with the citrate capped AgNP surface. Further, NMR relaxation-based experiments suggest that in addition to the dynamic exchange, a conformational rearrangement of the protein takes place upon binding to AgNP. The ultrastability of the AgNP-Ubq complex was found to be useful for its anti-microbial activity, which allowed the recycling of this complex multiple times without the loss of stability. Altogether, the study provides new insights into the mechanism of protein-silver nanoparticle interactions and opens up new avenues for its application in a wide range of systems. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03047a

Cyclometalated products of [(COE)(2)RhCl](2) and 1,3-(RSCH(2))(2)C(6)H(4) (R = (t)Bu, (i)Pr) Are Dimeric. Synthesis, molecular structures, and solution dynamics of [mu-ClRh(H)(RSCH(2))(2)C(6)H(3)-2,6](2).

PubMed

Evans, Daniel R; Huang, Mingsheng; Seganish, W Michael; Chege, Esther W; Lam, Yiu-Fai; Fettinger, James C; Williams, Tracie L

2002-05-20

Two tridentate thioether pincer ligands, 1,3-(RSCH(2))(2)C(6)H(4) (R = (t)()Bu, 1a; R = (i)()Pr, 1b) underwent cyclometalation using [(COE)(2)RhCl](2) in air/moisture-free benzene at room temperature. The resultant complexes, [mu-ClRh(H)(RSCH(2))(2)C(6)H(3)-2,6](2) (R = (t)Bu, 2a; R = (i)Pr, 2b) are dimeric both in the solid state and in solution. A battery of variable-temperature one- and two-dimensional (1)H NMR experiments showed conclusively that both complexes undergo dynamic exchange in solution. Exchange between two dimeric diastereomers of 2a in solution occurred via rotation about the Rh-C(ipso) bond. The dynamic exchange of 2b was significantly more complex as an additional exchange mechanism, sulfur inversion, occurred, which resulted in the exchange between several diastereomers in solution.

Second-order schedules of token reinforcement with pigeons: effects of fixed- and variable-ratio exchange schedules.

PubMed

Foster, T A; Hackenberg, T D; Vaidya, M

2001-09-01

Pigeons' key pecks produced food under second-order schedules of token reinforcement, with light-emitting diodes serving as token reinforcers. In Experiment 1, tokens were earned according to a fixed-ratio 50 schedule and were exchanged for food according to either fixed-ratio or variable-ratio exchange schedules, with schedule type varied across conditions. In Experiment 2, schedule type was varied within sessions using a multiple schedule. In one component, tokens were earned according to a fixed-ratio 50 schedule and exchanged according to a variable-ratio schedule. In the other component, tokens were earned according to a variable-ratio 50 schedule and exchanged according to a fixed-ratio schedule. In both experiments, the number of responses per exchange was varied parametrically across conditions, ranging from 50 to 400 responses. Response rates decreased systematically with increases in the fixed-ratio exchange schedules, but were much less affected by changes in the variable-ratio exchange schedules. Response rates were consistently higher under variable-ratio exchange schedules than tinder comparable fixed-ratio exchange schedules, especially at higher exchange ratios. These response-rate differences were due both to greater pre-ratio pausing and to lower local rates tinder the fixed-ratio exchange schedules. Local response rates increased with proximity to food under the higher fixed-ratio exchange schedules, indicative of discriminative control by the tokens.

Diurnal Variation in Gas Exchange: The Balance between Carbon Fixation and Water Loss.

PubMed

Matthews, Jack S A; Vialet-Chabrand, Silvere R M; Lawson, Tracy

2017-06-01

Stomatal control of transpiration is critical for maintaining important processes, such as plant water status, leaf temperature, as well as permitting sufficient CO 2 diffusion into the leaf to maintain photosynthetic rates ( A ). Stomatal conductance often closely correlates with A and is thought to control the balance between water loss and carbon gain. It has been suggested that a mesophyll-driven signal coordinates A and stomatal conductance responses to maintain this relationship; however, the signal has yet to be fully elucidated. Despite this correlation under stable environmental conditions, the responses of both parameters vary spatially and temporally and are dependent on species, environment, and plant water status. Most current models neglect these aspects of gas exchange, although it is clear that they play a vital role in the balance of carbon fixation and water loss. Future efforts should consider the dynamic nature of whole-plant gas exchange and how it represents much more than the sum of its individual leaf-level components, and they should take into consideration the long-term effect on gas exchange over time. © 2017 American Society of Plant Biologists. All Rights Reserved.

Structure, Kinetics, and Thermodynamics of the Aqueous Uranyl(VI) Cation

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

Kerisit, Sebastien N.; Liu, Chongxuan

2013-08-20

Molecular simulation techniques are employed to gain insights into the structural, kinetic, and thermodynamic properties of the uranyl(VI) cation (UO22+) in aqueous solution. The simulations make use of an atomistic potential model (force field) derived in this work and based on the model of Guilbaud and Wipff (Guilbaud, P.; Wipff, G. J. Mol. Struct. (THEOCHEM) 1996, 366, 55-63). Reactive flux and thermodynamic integration calculations show that the derived potential model yields predictions for the water exchange rate and free energy of hydration, respectively, that are in agreement with experimental data. The water binding energies, hydration shell structure, and self-diffusion coefficientmore » are also calculated and discussed. Finally, a combination of metadynamics and transition path sampling simulations is employed to probe the mechanisms of water exchange reactions in the first hydration shell of the uranyl ion. These atomistic simulations indicate, based on two-dimensional free energy surfaces, that water exchanges follow an associative interchange mechanism. The nature and structure of the water exchange transition states are also determined. The improved potential model is expected to lead to more accurate predictions of uranyl adsorption energies at mineral surfaces using potential-based molecular dynamics simulations.« less

Dynamical implications of bi-directional resource exchange within a meta-ecosystem.

PubMed

Messan, Marisabel Rodriguez; Kopp, Darin; Allen, Daniel C; Kang, Yun

2018-05-05

The exchange of resources across ecosystem boundaries can have large impacts on ecosystem structures and functions at local and regional scales. In this article, we develop a simple model to investigate dynamical implications of bi-directional resource exchanges between two local ecosystems in a meta-ecosystem framework. In our model, we assume that (1) Each local ecosystem acts as both a resource donor and recipient, such that one ecosystem donating resources to another results in a cost to the donating system and a benefit to the recipient; and (2) The costs and benefits of the bi-directional resource exchange between two ecosystems are correlated in a nonlinear fashion. Our model could apply to the resource interactions between terrestrial and aquatic ecosystems that are supported by the literature. Our theoretical results show that bi-directional resource exchange between two ecosystems can indeed generate complicated dynamical outcomes, including the coupled ecosystems having amensalistic, antagonistic, competitive, or mutualistic interactions, with multiple alternative stable states depending on the relative costs and benefits. In addition, if the relative cost for resource exchange for an ecosystem is decreased or the relative benefit for resource exchange for an ecosystem is increased, the production of that ecosystem would increase; however, depending on the local environment, the production of the other ecosystem may increase or decrease. We expect that our work, by evaluating the potential outcomes of resource exchange theoretically, can facilitate empirical evaluations and advance the understanding of spatial ecosystem ecology where resource exchanges occur in varied ecosystems through a complicated network. Copyright © 2018 Elsevier Inc. All rights reserved.

12 CFR Appendix A to Subpart A of... - Minimum Capital Components for Interest Rate and Foreign Exchange Rate Contracts

Code of Federal Regulations, 2011 CFR

2011-01-01

... interest rate and foreign exchange rate contracts are computed on the basis of the credit equivalent amounts of such contracts. Credit equivalent amounts are computed for each of the following off-balance... Equivalent Amounts a. The minimum capital components for interest rate and foreign exchange rate contracts...

Hetero-diffusion of Au epitaxy on stepped Ag(110) surface: Study of the jump rate and diffusion coefficient

NASA Astrophysics Data System (ADS)

Benlattar, M.; El koraychy, E.; Kotri, A.; Mazroui, M.

2017-12-01

We have used molecular dynamics simulations combined with an interatomic potential derived from the embedded atom method, to investigate the hetero-diffusion of Au adatom near a stepped Ag(110) surface with the height of one monoatomic layer. The activation energies for different diffusion processes, which occur on the terrace and near the step edge, are calculated both by molecular statics and molecular dynamics simulations. Static energies are found by the drag method, whereas the dynamic barriers are computed at high temperature from the Arrhenius plots. Our numerical results reveal that the jump process requires very high activation energy compared to the exchange process either on the terrace or near the step edge. In this work, other processes, such as upward and downward diffusion at step edges, have also been discussed.

Dynamics and thermodynamics of open chemical networks

NASA Astrophysics Data System (ADS)

Esposito, Massimiliano

Open chemical networks (OCN) are large sets of coupled chemical reactions where some of the species are chemostated (i.e. continuously restored from the environment). Cell metabolism is a notable example of OCN. Two results will be presented. First, dissipation in OCN operating in nonequilibrium steady-states strongly depends on the network topology (algebraic properties of the stoichiometric matrix). An application to oligosaccharides exchange dynamics performed by so-called D-enzymes will be provided. Second, at low concentration the dissipation of OCN is in general inaccurately predicted by deterministic dynamics (i.e. nonlinear rate equations for the species concentrations). In this case a description in terms of the chemical master equation is necessary. A notable exception is provided by so-called deficiency zero networks, i.e. chemical networks with no hidden cycles present in the graph of reactant complexes.

Strategies for Optimizing Water-Exchange Rates of Lanthanide-Based Contrast Agents for Magnetic Resonance Imaging

PubMed Central

Siriwardena-Mahanama, Buddhima N.; Allen, Matthew J.

2013-01-01

This review describes recent advances in strategies for tuning the water-exchange rates of contrast agents for magnetic resonance imaging (MRI). Water-exchange rates play a critical role in determining the efficiency of contrast agents; consequently, optimization of water-exchange rates, among other parameters, is necessary to achieve high efficiencies. This need has resulted in extensive research efforts to modulate water-exchange rates by chemically altering the coordination environments of the metal complexes that function as contrast agents. The focus of this review is coordination-chemistry-based strategies used to tune the water-exchange rates of lanthanide(III)-based contrast agents for MRI. Emphasis will be given to results published in the 21st century, as well as implications of these strategies on the design of contrast agents. PMID:23921796

Glucans monomer-exchange dynamics as an open chemical network

NASA Astrophysics Data System (ADS)

Rao, Riccardo; Lacoste, David; Esposito, Massimiliano

2015-12-01

We describe the oligosaccharides-exchange dynamics performed by the so-called D-enzymes on polysaccharides. To mimic physiological conditions, we treat this process as an open chemical network by assuming some of the polymer concentrations fixed (chemostatting). We show that three different long-time behaviors may ensue: equilibrium states, nonequilibrium steady states, and continuous growth states. We dynamically and thermodynamically characterize these states and emphasize the crucial role of conservation laws in identifying the chemostatting conditions inducing them.

Glucans monomer-exchange dynamics as an open chemical network

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

Rao, Riccardo, E-mail: riccardo.rao@uni.lu; Esposito, Massimiliano, E-mail: massimiliano.esposito@uni.lu; Lacoste, David

2015-12-28

We describe the oligosaccharides-exchange dynamics performed by the so-called D-enzymes on polysaccharides. To mimic physiological conditions, we treat this process as an open chemical network by assuming some of the polymer concentrations fixed (chemostatting). We show that three different long-time behaviors may ensue: equilibrium states, nonequilibrium steady states, and continuous growth states. We dynamically and thermodynamically characterize these states and emphasize the crucial role of conservation laws in identifying the chemostatting conditions inducing them.

Structure-Functional Basis of Ion Transport in Sodium–Calcium Exchanger (NCX) Proteins

PubMed Central

Giladi, Moshe; Shor, Reut; Lisnyansky, Michal; Khananshvili, Daniel

2016-01-01

The membrane-bound sodium–calcium exchanger (NCX) proteins shape Ca2+ homeostasis in many cell types, thus participating in a wide range of physiological and pathological processes. Determination of the crystal structure of an archaeal NCX (NCX_Mj) paved the way for a thorough and systematic investigation of ion transport mechanisms in NCX proteins. Here, we review the data gathered from the X-ray crystallography, molecular dynamics simulations, hydrogen–deuterium exchange mass-spectrometry (HDX-MS), and ion-flux analyses of mutants. Strikingly, the apo NCX_Mj protein exhibits characteristic patterns in the local backbone dynamics at particular helix segments, thereby possessing characteristic HDX profiles, suggesting structure-dynamic preorganization (geometric arrangements of catalytic residues before the transition state) of conserved α1 and α2 repeats at ion-coordinating residues involved in transport activities. Moreover, dynamic preorganization of local structural entities in the apo protein predefines the status of ion-occlusion and transition states, even though Na+ or Ca2+ binding modifies the preceding backbone dynamics nearby functionally important residues. Future challenges include resolving the structural-dynamic determinants governing the ion selectivity, functional asymmetry and ion-induced alternating access. Taking into account the structural similarities of NCX_Mj with the other proteins belonging to the Ca2+/cation exchanger superfamily, the recent findings can significantly improve our understanding of ion transport mechanisms in NCX and similar proteins. PMID:27879668

Structure-Functional Basis of Ion Transport in Sodium-Calcium Exchanger (NCX) Proteins.

PubMed

Giladi, Moshe; Shor, Reut; Lisnyansky, Michal; Khananshvili, Daniel

2016-11-22

The membrane-bound sodium-calcium exchanger (NCX) proteins shape Ca 2+ homeostasis in many cell types, thus participating in a wide range of physiological and pathological processes. Determination of the crystal structure of an archaeal NCX (NCX_Mj) paved the way for a thorough and systematic investigation of ion transport mechanisms in NCX proteins. Here, we review the data gathered from the X-ray crystallography, molecular dynamics simulations, hydrogen-deuterium exchange mass-spectrometry (HDX-MS), and ion-flux analyses of mutants. Strikingly, the apo NCX_Mj protein exhibits characteristic patterns in the local backbone dynamics at particular helix segments, thereby possessing characteristic HDX profiles, suggesting structure-dynamic preorganization (geometric arrangements of catalytic residues before the transition state) of conserved α₁ and α₂ repeats at ion-coordinating residues involved in transport activities. Moreover, dynamic preorganization of local structural entities in the apo protein predefines the status of ion-occlusion and transition states, even though Na⁺ or Ca 2+ binding modifies the preceding backbone dynamics nearby functionally important residues. Future challenges include resolving the structural-dynamic determinants governing the ion selectivity, functional asymmetry and ion-induced alternating access. Taking into account the structural similarities of NCX_Mj with the other proteins belonging to the Ca 2+ /cation exchanger superfamily, the recent findings can significantly improve our understanding of ion transport mechanisms in NCX and similar proteins.

Dynamics of carbon dioxide exchange of a wheat community grown in a semi-closed environment

NASA Technical Reports Server (NTRS)

Corey, Kenneth A.

1989-01-01

A wheat (Triticum aestivum Yecora Rojo) community was grown in the semi-closed conditions of the NASA/KSC Biomass Production Chamber (BPC). Experiments were conducted to determine whole community carbon dioxide exchange rates as influenced by growth and development, carbon dioxide concentration, time within the photoperiod, irradiance, and temperature. Plants were grown at a population of about 1500 per sq meter using a 20 hour light/4 hour dark daily regime. Light was supplied by HPS vapor lamps and irradiance was maintained in the range of 590 to 675 mu mol per sq meter. The temperature regime was 20 C light/16 C dark and nutrients were supplied hydroponically as a thin film. Fractional interception of PPF by the community increased rapidly during growth reaching a maximum of 0.96, 24 days after planting. This time corresponded to canopy closure and maximum rates of net photosynthesis (NP). Net daily CO2 utilization rates were calculated to day 48 and a 4th order regression equation integrated to obtain total moles of CO2 fixed by the community. This procedure may be useful for monitoring and prediction of biomass yields in a closed ecology life support system (CELSS).

Ion cyclotron instability at Io: Hybrid simulation results compared to in situ observations

NASA Astrophysics Data System (ADS)

Šebek, Ondřej; Trávníček, Pavel M.; Walker, Raymond J.; Hellinger, Petr

2016-08-01

We present analysis of global three-dimensional hybrid simulations of Io's interaction with Jovian magnetospheric plasma. We apply a single-species model with simplified neutral-plasma chemistry and downscale Io in order to resolve the ion kinetic scales. We consider charge exchange, electron impact ionization, and photoionization by using variable rates of these processes to investigate their impact. Our results are in a good qualitative agreement with the in situ magnetic field measurements for five Galileo flybys around Io. The hybrid model describes ion kinetics self-consistently. This allows us to assess the distribution of temperature anisotropies around Io and thereby determine the possible triggering mechanism for waves observed near Io. We compare simulated dynamic spectra of magnetic fluctuations with in situ observations made by Galileo. Our results are consistent with both the spatial distribution and local amplitude of magnetic fluctuations found in the observations. Cyclotron waves, triggered probably by the growth of ion cyclotron instability, are observed mainly downstream of Io and on the flanks in regions farther from Io where the ion pickup rate is relatively low. Growth of the ion cyclotron instability is governed mainly by the charge exchange rate.

Teaching Exchange Rate Risk Using London's Gherkin Building: How Investors Were in (and out of) a Pickle

ERIC Educational Resources Information Center

Jones, Adam T.; Sackley, William H.; Watson, Ethan D.

2017-01-01

In this teaching note, the authors use an iconic London building, the Gherkin, as a motivation to understand exchange rates, cross exchange rates, and unhedged exchange rate risk. The famous tower was constructed in the early 2000s by Swiss Re, an insurance company, and then sold to investors as part of a sale-leaseback deal in early 2007.…

Investigating the asymmetric relationship between inflation-output growth exchange rate changes

NASA Astrophysics Data System (ADS)

Chu, Jenq Fei; Sek, Siok Kun

2017-08-01

The relationship between inflation-output growth or output variation has long been studied. In this study, we extend the investigation under two exchange rate flexibility/regime in four Asian countries (Indonesia, Korea, Philippines and Thailand) that have experienced drastic exchange rate regime changes aftermath the financial crisis of 1997. These countries have switched from fixed/rigid exchange rate regime to flexible exchange rate and inflation targeting (IT) regime after the crisis. Our main objective is to compare the inflation-output trade-off relationship in the pre-IT and post-IT periods as a tool to evaluate the efficiency of monetary policy. A nonlinear autoregressive distributed lags (NARDL) model is applied to capture the asymmetric effects of exchange rate changes (increases and decreases). The data ranging from 1981M1 onwards till 2016M3. Our results show that exchange rate has asymmetric effect on inflation both short-run and long-run with larger impact in the post-IT period under flexible regime. Depreciation of exchange rate has leads to higher inflation. Furthermore, we find evidences on the relationship between inflation and growth in both short-run and long-run, but the trade-off only detected in the short run both in the pre- and post-IT periods.

The hydration of amides in helices; a comprehensive picture from molecular dynamics, IR, and NMR

PubMed Central

Walsh, Scott T.R.; Cheng, Richard P.; Wright, Wayne W.; Alonso, Darwin O.V.; Daggett, Valerie; Vanderkooi, Jane M.; DeGrado, William F.

2003-01-01

We examined the hydration of amides of α3D, a simple, designed three-helix bundle protein. Molecular dynamics calculations show that the amide carbonyls on the surface of the protein tilt away from the helical axis to interact with solvent water, resulting in a lengthening of the hydrogen bonds on this face of the helix. Water molecules are bonded to these carbonyl groups with partial occupancy (∼50%–70%), and their interaction geometries show a large variation in their hydrogen bond lengths and angles on the nsec time scale. This heterogeneity is reflected in the carbonyl stretching vibration (amide I′ band) of a group of surface Ala residues. The surface-exposed amides are broad, and shift to lower frequency (reflecting strengthening of the hydrogen bonds) as the temperature is decreased. By contrast, the amide I′ bands of the buried 13C-labeled Leu residues are significantly sharper and their frequencies are consistent with the formation of strong hydrogen bonds, independent of temperature. The rates of hydrogen-deuterium exchange and the proton NMR chemical shifts of the helical amide groups also depend on environment. The partial occupancy of the hydration sites on the surface of helices suggests that the interaction is relatively weak, on the order of thermal energy at room temperature. One unexpected feature that emerged from the dynamics calculations was that a Thr side chain subtly disrupted the helical geometry 4–7 residues N-terminal in sequence, which was reflected in the proton chemical shifts and the rates of amide proton exchange for several amides that engage in a mixed 310/α/π-helical conformation. PMID:12592022

Modeling and estimating the jump risk of exchange rates: Applications to RMB

NASA Astrophysics Data System (ADS)

Wang, Yiming; Tong, Hanfei

2008-11-01

In this paper we propose a new type of continuous-time stochastic volatility model, SVDJ, for the spot exchange rate of RMB, and other foreign currencies. In the model, we assume that the change of exchange rate can be decomposed into two components. One is the normally small-cope innovation driven by the diffusion motion; the other is a large drop or rise engendered by the Poisson counting process. Furthermore, we develop a MCMC method to estimate our model. Empirical results indicate the significant existence of jumps in the exchange rate. Jump components explain a large proportion of the exchange rate change.

The Dynamics of Multilateral Exchange

NASA Astrophysics Data System (ADS)

Hausken, Kjell; Moxnes, John F.

The article formulates a dynamic mathematical model where arbitrarily many players produce, consume, exchange, loan, and deposit arbitrarily many goods over time to maximize utility. Consuming goods constitutes a benefit, and producing, exporting, and loaning away goods constitute a cost. Utilities are benefits minus costs, which depend on the exchange ratios and bargaining functions. Three-way exchange occurs when one player acquires, through exchange, one good from another player with the sole purpose of using this good to exchange against the desired good from a third player. Such a triple handshake is not merely a set of double handshakes since the player assigns no interest to the first good in his benefit function. Cognitive and organization costs increase dramatically for higher order exchanges. An exchange theory accounting for media of exchange follows from simple generalization of two-way exchange. The examples of r-way exchange are the triangle trade between Africa, the USA, and England in the 17th and 18th centuries, the hypothetical hypercycle involving RNAs as players and enzymes as goods, and reaction-diffusion processes. The emergence of exchange, and the role of trading agents are discussed. We simulate an example where two-way exchange gives zero production and zero utility, while three-way exchange causes considerable production and positive utility. Maximum utility for each player is reached when exchanges of the same order as the number of players in society are allowed. The article merges micro theory and macro theory within the social, natural, and physical sciences.

Asia-Pacific Economic Update. Volume 1. Economic Strategy, Context and Performance

DTIC Science & Technology

2002-01-01

deficits and rigid exchange rate regimes contributed to financial turbulence and a disorderly free-fall of Asian foreign exchange rates . Floating exchange rate regimes are needed to optimize free international capital markets.

Surface nanobubble nucleation dynamics during water-ethanol exchange

NASA Astrophysics Data System (ADS)

Chan, Chon U.; Ohl, Claus-Dieter

2015-11-01

Water-ethanol exchange has been a promising nucleation method for surface attached nanobubbles since their discovery. In this process, water and ethanol displace each other sequentially on a substrate. As the gas solubility is 36 times higher in ethanol than water, it was suggested that the exchange process leads to transient supersaturation and is responsible for the nanobubble nucleation. In this work, we visualize the nucleation dynamics by controllably mixing water and ethanol. It depicts the temporal evolution of the conventional exchange in a single field of view, detailing the conditions for surface nanobubble nucleation and the flow field that influences their spatial organization. This technique can also pattern surface nanobubbles with variable size distribution.

Microcanonical model for interface formation

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

Rucklidge, A.; Zaleski, S.

1988-04-01

We describe a new cellular automaton model which allows us to simulate separation of phases. The model is an extension of existing cellular automata for the Ising model, such as Q2R. It conserves particle number and presents the qualitative features of spinodal decomposition. The dynamics is deterministic and does not require random number generators. The spins exchange energy with small local reservoirs or demons. The rate of relaxation to equilibrium is investigated, and the results are compared to the Lifshitz-Slyozov theory.

International Trade of Wood Pellets (Brochure)

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

Not Available

The production of wood pellets has increased dramatically in recent years due in large part to aggressive emissions policy in the European Union; the main markets that currently supply the European market are North America and Russia. However, current market circumstances and trade dynamics could change depending on the development of emerging markets, foreign exchange rates, and the evolution of carbon policies. This fact sheet outlines the existing and potential participants in the wood pellets market, along with historical data on production, trade, and prices.

Experimental Validation of a Time-Accurate Finite Element Model for Coupled Multibody Dynamics and Liquid Sloshing

DTIC Science & Technology

2007-04-16

velocity of the fluid mesh, P is the relative pressure, xr is the position vector, τ is the deviatoric stress tensor, D is the rate of deformation...corresponds to a slip factor of zero. The slip factor determines how much of the fluid and structure forces are mutually exchanged. Equations 22 and 23...updated from last to first. viii.Average the fluid pressure (This step eliminates the pressure checker-boarding effect and allows use of equal

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

DTIC Science & Technology

1985-08-01

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

75 FR 7301 - Self-Regulatory Organizations; Chicago Board Options Exchange, Incorporated; Notice of Filing and...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-02-18

... difference is that the Exchange used clearing firm floating monthly rate information for the month of... account changes in clearing firm floating monthly rates for the month of February 2010. The Exchange... fees are currently set at the indicative lease rate (as defined below) for January 2010. The Exchange...

75 FR 11962 - Self-Regulatory Organizations; Chicago Board Options Exchange, Incorporated; Notice of Filing and...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-03-12

... difference is that the Exchange used clearing firm floating monthly rate information for the month of March... changes in clearing firm floating monthly rates for the month of March 2010. The Exchange believes that... equal to the indicative lease rate for March 2010 (which is $4,875). Specifically, the Exchange proposes...

75 FR 3951 - Self-Regulatory Organizations; Chicago Board Options Exchange, Incorporated; Notice of Filing and...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-01-25

... difference is that the Exchange used clearing firm floating monthly rate information for the month of January... changes in clearing firm floating monthly rates for the month of January 2010. The Exchange believes that... fees are currently set at the indicative lease rate (as defined below) for December 2009. The Exchange...

Dynamic monitoring of blood-brain barrier integrity using water exchange index (WEI) during mannitol and CO2 challenges in mouse brain.

PubMed

Huang, Shuning; Farrar, Christian T; Dai, Guangping; Kwon, Seon Joo; Bogdanov, Alexei A; Rosen, Bruce R; Kim, Young R

2013-04-01

The integrity of the blood-brain barrier (BBB) is critical to normal brain function. Traditional techniques for the assessment of BBB disruption rely heavily on the spatiotemporal analysis of extravasating contrast agents. However, such methods based on the leakage of relatively large molecules are not suitable for the detection of subtle BBB impairment or for the performance of repeated measurements in a short time frame. Quantification of the water exchange rate constant (WER) across the BBB using strictly intravascular contrast agents could provide a much more sensitive method for the quantification of the BBB integrity. To estimate WER, we have recently devised a powerful new method using a water exchange index (WEI) biomarker and demonstrated BBB disruption in an acute stroke model. Here, we confirm that WEI is sensitive to even very subtle changes in the integrity of the BBB caused by: (i) systemic hypercapnia and (ii) low doses of a hyperosmolar solution. In addition, we have examined the sensitivity and accuracy of WEI as a biomarker of WER using computer simulation. In particular, the dependence of the WEI-WER relation on changes in vascular blood volume, T1 relaxation of cellular magnetization and transcytolemmal water exchange was explored. Simulated WEI was found to vary linearly with WER for typically encountered exchange rate constants (1-4 Hz), regardless of the blood volume. However, for very high WER (>5 Hz), WEI became progressively more insensitive to increasing WER. The incorporation of transcytolemmal water exchange, using a three-compartment tissue model, helped to extend the linear WEI regime to slightly higher WER, but had no significant effect for most physiologically important WERs (WER < 4 Hz). Variation in cellular T1 had no effect on WEI. Using both theoretical and experimental approaches, our study validates the utility of the WEI biomarker for the monitoring of BBB integrity. Copyright © 2012 John Wiley & Sons, Ltd.

Restoring hydrological and biogeochemical ecosystem services in streams: how can science inform practice?

NASA Astrophysics Data System (ADS)

Lautz, L.; Gordon, R.; Daniluk, T.; Zimmer, M. A.; Endreny, T. A.; McGrath, K.

2014-12-01

Society is increasingly recognizing the value of stream ecosystem functions, as evidenced by the enormous economic investment being made in stream restoration across the United States. Stream restoration projects have a variety of goals, including improvement in water quality and in-stream habitat. Popular approaches to restoration (such as Natural Channel Design, or NCD) aim to move degraded streams along a trajectory toward a dynamic ecological endpoint that represents natural conditions. Project designs primarily focus on channel form and function, but stream-groundwater exchanges of water and solutes are not typically a design consideration, although a primary component of fully functioning stream ecosystems. Here, we synthesize results from field investigations of the impact of NCD stream restoration on stream-groundwater exchanges by (1) comparing restored sites to reference reaches, which serve as the basis for the restoration design, (2) characterizing multiple restored sites to determine universal characteristics of streams restored by NCD, and (3) monitoring a stream pre- and post- restoration. NCD restoration creates hot spots of rapid hyporheic exchange upstream of channel spanning structures, with water fluxes across the bed interface up to an order of magnitude higher than at pre-restoration or reference reaches. Elevated flux rates result in short hyporheic residence times, which are not sufficiently long to generate net changes in nutrient concentrations. Hot spots of biogeochemical transformations are instead located around secondary bedforms, such as pool-riffle sequences, where gross water exchange rates are more moderate. Reference reaches show greater evidence of groundwater discharge to the hyporheic zone relative to restored reaches, although observations before and after restoration suggest NCD can modify the spatial extent of groundwater discharge zones. Gross water exchange across the streambed interface along restored reaches is a small percentage of stream discharge, suggesting the primary impact of restoration on stream-groundwater exchange is promoting biochemical heterogeneity in the subsurface, rather than longitudinal net changes in stream solute concentrations. Results inform future design to achieve restoration goals.

The 1994 Economic Crisis in Turkey

DTIC Science & Technology

2002-06-01

began to influence the interest rates and foreign exchange rates 36 more than the Central Bank. These developments, as a result, forced the Central Bank...capital to finance the public deficit, increasing international creditors’ influence on the interest rates and foreign exchange rates . Increasing foreign...influence on both the interest rates and foreign exchange rates , however, significantly reduced the government’s independence in designing monetary

Space shuttle launch vehicle performance trajectory, exchange ratios, and dispersion analysis

NASA Technical Reports Server (NTRS)

Toelle, R. G.; Blackwell, D. L.; Lott, L. N.

1973-01-01

A baseline space shuttle performance trajectory for Mission 3A launched from WTR has been generated. Design constraints of maximum dynamic pressure, longitudinal acceleration, and delivered payload were satisfied. Payload exchange ratios are presented with explanation on use. Design envelopes of dynamic pressure, SRB staging point, aerodynamic heating and flight performance reserves are calculated and included.

Combined Steady-State and Dynamic Heat Exchanger Experiment

ERIC Educational Resources Information Center

Luyben, William L.; Tuzla, Kemal; Bader, Paul N.

2009-01-01

This paper describes a heat-transfer experiment that combines steady-state analysis and dynamic control. A process-water stream is circulated through two tube-in-shell heat exchangers in series. In the first, the process water is heated by steam. In the second, it is cooled by cooling water. The equipment is pilot-plant size: heat-transfer areas…

Cooperative Team Networks

DTIC Science & Technology

2016-06-01

team processes, such as identifying motifs of dynamic communication exchanges which goes well beyond simple dyadic and triadic configurations; as well...new metrics and ways to formulate team processes, such as identifying motifs of dynamic communication exchanges which goes well beyond simple dyadic ...sensing, communication , information, and decision networks - Darryl Ahner (AFIT: Air Force Inst Tech) Panel Session: Mathematical Models of

Diffusive and Arrestedlike Dynamics in Currency Exchange Markets

NASA Astrophysics Data System (ADS)

Clara-Rahola, J.; Puertas, A. M.; Sánchez-Granero, M. A.; Trinidad-Segovia, J. E.; de las Nieves, F. J.

2017-02-01

This work studies the symmetry between colloidal dynamics and the dynamics of the Euro-U.S. dollar currency exchange market (EURUSD). We consider the EURUSD price in the time range between 2001 and 2015, where we find significant qualitative symmetry between fluctuation distributions from this market and the ones belonging to colloidal particles in supercooled or arrested states. In particular, we find that models used for arrested physical systems are suitable for describing the EURUSD fluctuation distributions. Whereas the corresponding mean-squared price displacement (MSPD) to the EURUSD is diffusive for all years, when focusing in selected time frames within a day, we find a two-step MSPD when the New York Stock Exchange market closes, comparable to the dynamics in supercooled systems. This is corroborated by looking at the price correlation functions and non-Gaussian parameters and can be described by the theoretical model. We discuss the origin and implications of this analogy.

The loss rates of O+ in the inner magnetosphere caused by both magnetic field line curvature scattering and charge exchange reactions

NASA Astrophysics Data System (ADS)

Ji, Y.; Shen, C.

2014-03-01

With consideration of magnetic field line curvature (FLC) pitch angle scattering and charge exchange reactions, the O+ (>300 keV) in the inner magnetosphere loss rates are investigated by using an eigenfunction analysis. The FLC scattering provides a mechanism for the ring current O+ to enter the loss cone and influence the loss rates caused by charge exchange reactions. Assuming that the pitch angle change is small for each scattering event, the diffusion equation including a charge exchange term is constructed and solved; the eigenvalues of the equation are identified. The resultant loss rates of O+ are approximately equal to the linear superposition of the loss rate without considering the charge exchange reactions and the loss rate associated with charge exchange reactions alone. The loss time is consistent with the observations from the early recovery phases of magnetic storms.

Contrasting dynamics of leaf potential and gas exchange during progressive drought cycles and recovery in Amorpha fruticosa and Robinia pseudoacacia.

PubMed

Yan, Weiming; Zheng, Shuxia; Zhong, Yangquanwei; Shangguan, Zhouping

2017-06-30

Leaf gas exchange is closely associated with water relations; however, less attention has been given to this relationship over successive drought events. Dynamic changes in gas exchange and water potential in the seedlings of two woody species, Amorpha fruticosa and Robinia pseudoacacia, were monitored during recurrent drought. The pre-dawn leaf water potential declined in parallel with gas exchange in both species, and sharp declines in gas exchange occurred with decreasing water potential. A significant correlation between pre-dawn water potential and gas exchange was observed in both species and showed a right shift in R. pseudoacacia in the second drought. The results suggested that stomatal closure in early drought was mediated mainly by elevated foliar abscisic acid (ABA) in R. pseudoacacia, while a shift from ABA-regulated to leaf-water-potential-driven stomatal closure was observed in A. fruticosa. After re-watering, the pre-dawn water potential recovered quickly, whereas stomatal conductance did not fully recover from drought in R. pseudoacacia, which affected the ability to tightly control transpiration post-drought. The dynamics of recovery from drought suggest that stomatal behavior post-drought may be restricted mainly by hydraulic factors, but non-hydraulic factors may also be involved in R. pseudoacacia.

Studies on the application of temperature-responsive ion exchange polymers with whey proteins.

PubMed

Maharjan, Pankaj; Campi, Eva M; De Silva, Kirthi; Woonton, Brad W; Jackson, W Roy; Hearn, Milton T W

2016-03-18

Several new types of temperature-responsive ion exchange resins of different polymer composition have been prepared by grafting the products from the co-polymerisation of N-phenylacrylamide, N-iso-propylacrylamide and acrylic acid derivatives onto cross-linked agarose. Analysis of the binding isotherms for these different resins obtained under batch adsorption conditions indicated that the resin based on N-iso-propylacrylamide containing 5% (w/w) N-phenylacrylamide and 5% (w/w) acrylic acid resulted in the highest adsorption capacity, Bmax, for the whey protein, bovine lactoferrin, e.g. 14 mg bovine lactoferrin/mL resin at 4 °C and 62 mg bovine lactoferrin/mL resin at 40 °C, respectively. Under dynamic loading conditions at 40 °C, 94% of the loaded bovine lactoferrin on a normalised mg protein per mL resin basis was adsorbed by this new temperature-responsive ion-exchanger, and 76% was eluted by a single cycle temperature shift to 4 °C without varying the composition of the 10mM sodium dihydrogen phosphate buffer, pH 6.5, or the flow rate. The binding characteristics of these different ion exchange resins with bovine lactoferrin were also compared to results obtained using other resins based on N-isopropylacrylamide but contained N-tert-butylacrylamide rather than N-phenylacrylamide, where the corresponding dynamic capture and release properties for bovine lactoferrin required different temperature conditions of 20 °C and 50 °C, respectively for optimal desorption/adsorption. The cationic protein, bovine lactoperoxidase, was also adsorbed and desorbed with these temperature-responsive resins under similar conditions of changing temperature, whereas the anionic protein, bovine β-lactoglobulin, was not adsorbed under this regime of temperature conditions but instead eluted in the flow-through. Copyright © 2016 Elsevier B.V. All rights reserved.

Dynamics of chest wall volume regulation during constant work rate exercise in patients with chronic obstructive pulmonary disease

PubMed Central

Takara, L.S.; Cunha, T.M.; Barbosa, P.; Rodrigues, M.K.; Oliveira, M.F.; Nery, L.E.; Neder, J.A.

2012-01-01

This study evaluated the dynamic behavior of total and compartmental chest wall volumes [(VCW) = rib cage (VRC) + abdomen (VAB)] as measured breath-by-breath by optoelectronic plethysmography during constant-load exercise in patients with stable chronic obstructive pulmonary disease. Thirty males (GOLD stages II-III) underwent a cardiopulmonary exercise test to the limit of tolerance (Tlim) at 75% of peak work rate on an electronically braked cycle ergometer. Exercise-induced dynamic hyperinflation was considered to be present when end-expiratory (EE) VCW increased in relation to resting values. There was a noticeable heterogeneity in the patterns of VCW regulation as EEVCW increased non-linearly in 17/30 “hyperinflators” and decreased in 13/30 “non-hyperinflators” (P < 0.05). EEVAB decreased slightly in 8 of the “hyperinflators”, thereby reducing and slowing the rate of increase in end-inspiratory (EI) VCW (P < 0.05). In contrast, decreases in EEVCW in the “non-hyperinflators” were due to the combination of stable EEVRC with marked reductions in EEVAB. These patients showed lower EIVCW and end-exercise dyspnea scores but longer Tlim than their counterparts (P < 0.05). Dyspnea increased and Tlim decreased non-linearly with a faster rate of increase in EIVCW regardless of the presence or absence of dynamic hyperinflation (P < 0.001). However, no significant between-group differences were observed in metabolic, pulmonary gas exchange and cardiovascular responses to exercise. Chest wall volumes are continuously regulated during exercise in order to postpone (or even avoid) their migration to higher operating volumes in patients with COPD, a dynamic process that is strongly dependent on the behavior of the abdominal compartment. PMID:23250012

Temperature dependence of exchange bias in (NiFe/IrMn)n multilayer films studied through static and dynamic techniques

NASA Astrophysics Data System (ADS)

Adams, Daniel J.; Khanal, Shankar; Khan, Mohammad Asif; Maksymov, Artur; Spinu, Leonard

2018-05-01

The in-plane temperature dependence of exchange bias was studied through both dc magnetometry and ferromagnetic resonance spectroscopy in a series of [NiFe/IrMn]n multilayer films, where n is the number of layer repetitions. Major hysteresis loops were recorded in the temperature range of 300 K to 2 K to reveal the effect of temperature on the exchange bias in the static regime while temperature-dependent continuous-wave ferromagnetic resonance for frequencies from 3 to 16 GHz was used to determine the exchange bias dynamically. Strong divergence between the values of exchange bias determined using the two different types of measurements as well as a peak in temperature dependence of the resonance linewidth were observed. These results are explained in terms of the slow-relaxer mechanism.

Principles of establishing material cycling with a high degree of closure in the experimental model of a BTLSS intended for a rated "fraction of a human"

NASA Astrophysics Data System (ADS)

Tikhomirov, Alexander A.; Ushakova, Sofya; Velichko, Vladimir; Tikhomirova, Natalia; Shikhov, Valentin; Trifonov, Sergey V.

2016-07-01

A promising way to develop future biotechnical life support systems (BTLSS) is to construct experimental models and establish the cycling intended for a fraction of a human. Being of relatively low cost, such models provide an opportunity to test effectively closed process that could be further transferred to the real BTLSS with humans. Researchers of the IBP SB RAS are developing an adequate BTLSS model with the loops closed to a high degree. To attain high closure of mass exchange processes, plants in the phototrophic compartment are cultivated under intensive lighting conditions, created by using modern LED irradiators of enhanced power, equipped with lens optics. The higher plant compartment has been renewed and broadened by including soybean plants, which improve the vegetable part of the human diet and make it more diverse. It is very important that the operation of the physicochemical installation for waste mineralization fully matches the composition of the atmosphere of plant growth chambers: the purified gaseous components of this installation enter the common atmosphere of the system, without causing any deviations from the norm in the gaseous composition. This proves the eco-friendliness of the developed physicochemical method of waste mineralization and shows that the gaseous components resulting from waste mineralization can be included in the system mass exchange. A system for including human respiration into the gas exchange of the BTLSS has been developed and tested; the associated gas exchange and water exchange dynamics have been analyzed. Results of the functioning of the experimental model of the BTLSS for several months are proposed for discussion in order to get insight into the formation of dynamic characteristics of cycling processes and factors determining them. The study was supported by the grant of the Russian Science Foundation (Project 14-14-00599) and carried out at the IBP SB RAS.

Chemical exchange rotation transfer imaging of intermediate-exchanging amines at 2 ppm.

PubMed

Zu, Zhongliang; Louie, Elizabeth A; Lin, Eugene C; Jiang, Xiaoyu; Does, Mark D; Gore, John C; Gochberg, Daniel F

2017-10-01

Chemical exchange saturation transfer (CEST) imaging of amine protons exchanging at intermediate rates and whose chemical shift is around 2 ppm may provide a means of mapping creatine. However, the quantification of this effect may be compromised by the influence of overlapping CEST signals from fast-exchanging amines and hydroxyls. We aimed to investigate the exchange rate filtering effect of a variation of CEST, named chemical exchange rotation transfer (CERT), as a means of isolating creatine contributions at around 2 ppm from other overlapping signals. Simulations were performed to study the filtering effects of CERT for the selection of transfer effects from protons of specific exchange rates. Control samples containing the main metabolites in brain, bovine serum albumin (BSA) and egg white albumen (EWA) at their physiological concentrations and pH were used to study the ability of CERT to isolate molecules with amines at 2 ppm that exchange at intermediate rates, and corresponding methods were used for in vivo rat brain imaging. Simulations showed that exchange rate filtering can be combined with conventional filtering based on chemical shift. Studies on samples showed that signal contributions from creatine can be separated from those of other metabolites using this combined filter, but contributions from protein amines may still be significant. This exchange filtering can also be used for in vivo imaging. CERT provides more specific quantification of amines at 2 ppm that exchange at intermediate rates compared with conventional CEST imaging. Copyright © 2017 John Wiley & Sons, Ltd.

Exchange-Mediated Contrast Agents for Spin-Lock Imaging

PubMed Central

Cobb, Jared G.; Xie, Jingping; Li, Ke; Gochberg, Daniel F.; Gore, John C.

2011-01-01

Measurements of relaxation rates in the rotating frame with spin-locking (SL) techniques are sensitive to substances with exchanging protons with appropriate chemical shifts. We develop a novel approach to exchange rate selective imaging based on measured T1ρ dispersion with applied locking field strength, and demonstrate the method on samples containing the X-ray contrast agent Iohexol (IO) with and without cross-linked bovine serum albumin (BSA). T1ρ dispersion of water in the phantoms was measured with a Varian 9.4T magnet by an on-resonance SL pulse with fast spin-echo readout, and the results used to estimate exchange rates. The IO phantom alone gave a fitted exchange rate of ~1 kHz, BSA alone was ~11 kHz, and in combination gave rates in between. By using these estimated rates, we demonstrate how a novel SL imaging method may be used to enhance contrast due to the presence of a contrast agent whose protons have specific exchange rates. PMID:21954094

Solution structure and intramolecular exchange of methyl-cytosine binding domain protein 4 (MBD4) on DNA suggests a mechanism to scan for mCpG/TpG mismatches

PubMed Central

Walavalkar, Ninad M.; Cramer, Jason M.; Buchwald, William A.; Scarsdale, J. Neel; Williams, David C.

2014-01-01

Unlike other members of the methyl-cytosine binding domain (MBD) family, MBD4 serves as a potent DNA glycosylase in DNA mismatch repair specifically targeting mCpG/TpG mismatches arising from spontaneous deamination of methyl-cytosine. The protein contains an N-terminal MBD (MBD4MBD) and a C-terminal glycosylase domain (MBD4GD) separated by a long linker. This arrangement suggests that the MBD4MBD either directly augments enzymatic catalysis by the MBD4GD or targets the protein to regions enriched for mCpG/TpG mismatches. Here we present structural and dynamic studies of MBD4MBD bound to dsDNA. We show that MBD4MBD binds with a modest preference formCpG as compared to mismatch, unmethylated and hydroxymethylated DNA. We find that while MBD4MBD exhibits slow exchange between molecules of DNA (intermolecular exchange), the domain exhibits fast exchange between two sites in the same molecule of dsDNA (intramolecular exchange). Introducing a single-strand defect between binding sites does not greatly reduce the intramolecular exchange rate, consistent with a local hopping mechanism for moving along the DNA. These results support a model in which the MBD4MBD4 targets the intact protein to mCpG islands and promotes scanning by rapidly exchanging between successive mCpG sites which facilitates repair of nearby mCpG/TpG mismatches by the glycosylase domain. PMID:25183517

Dynamic studies of H-Ras•GTPγS interactions with nucleotide exchange factor Sos reveal a transient ternary complex formation in solution.

PubMed

Vo, Uybach; Vajpai, Navratna; Embrey, Kevin J; Golovanov, Alexander P

2016-07-14

The cycling between GDP- and GTP- bound forms of the Ras protein is partly regulated by the binding of Sos. The structural/dynamic behavior of the complex formed between activated Sos and Ras at the point of the functional cycle where the nucleotide exchange is completed has not been described to date. Here we show that solution NMR spectra of H-Ras∙GTPγS mixed with a functional fragment of Sos (Sos(Cat)) at a 2:1 ratio are consistent with the formation of a rather dynamic assembly. H-Ras∙GTPγS binding was in fast exchange on the NMR timescale and retained a significant degree of molecular tumbling independent of Sos(Cat), while Sos(Cat) also tumbled largely independently of H-Ras. Estimates of apparent molecular weight from both NMR data and SEC-MALS revealed that, at most, only one H-Ras∙GTPγS molecule appears stably bound to Sos. The weak transient interaction between Sos and the second H-Ras∙GTPγS may provide a necessary mechanism for complex dissociation upon the completion of the native GDP → GTP exchange reaction, but also explains measurable GTP → GTP exchange activity of Sos routinely observed in in vitro assays that use fluorescently-labelled analogs of GTP. Overall, the data presents the first dynamic snapshot of Ras functional cycle as controlled by Sos.

Quantitative analysis of protein-ligand interactions by NMR.

PubMed

Furukawa, Ayako; Konuma, Tsuyoshi; Yanaka, Saeko; Sugase, Kenji

2016-08-01

Protein-ligand interactions have been commonly studied through static structures of the protein-ligand complex. Recently, however, there has been increasing interest in investigating the dynamics of protein-ligand interactions both for fundamental understanding of the underlying mechanisms and for drug development. NMR is a versatile and powerful tool, especially because it provides site-specific quantitative information. NMR has widely been used to determine the dissociation constant (KD), in particular, for relatively weak interactions. The simplest NMR method is a chemical-shift titration experiment, in which the chemical-shift changes of a protein in response to ligand titration are measured. There are other quantitative NMR methods, but they mostly apply only to interactions in the fast-exchange regime. These methods derive the dissociation constant from population-averaged NMR quantities of the free and bound states of a protein or ligand. In contrast, the recent advent of new relaxation-based experiments, including R2 relaxation dispersion and ZZ-exchange, has enabled us to obtain kinetic information on protein-ligand interactions in the intermediate- and slow-exchange regimes. Based on R2 dispersion or ZZ-exchange, methods that can determine the association rate, kon, dissociation rate, koff, and KD have been developed. In these approaches, R2 dispersion or ZZ-exchange curves are measured for multiple samples with different protein and/or ligand concentration ratios, and the relaxation data are fitted to theoretical kinetic models. It is critical to choose an appropriate kinetic model, such as the two- or three-state exchange model, to derive the correct kinetic information. The R2 dispersion and ZZ-exchange methods are suitable for the analysis of protein-ligand interactions with a micromolar or sub-micromolar dissociation constant but not for very weak interactions, which are typical in very fast exchange. This contrasts with the NMR methods that are used to analyze population-averaged NMR quantities. Essentially, to apply NMR successfully, both the type of experiment and equation to fit the data must be carefully and specifically chosen for the protein-ligand interaction under analysis. In this review, we first explain the exchange regimes and kinetic models of protein-ligand interactions, and then describe the NMR methods that quantitatively analyze these specific interactions. Copyright © 2016 Elsevier B.V. All rights reserved.

Sparseness and Roughness of Foreign Exchange Rates

NASA Astrophysics Data System (ADS)

Vandewalle, N.; Ausloos, M.

An accurate multiaffine analysis of 23 foreign currency exchange rates has been performed. The roughness exponent H1 which characterizes the excursion of the exchange rate has been numerically measured. The degree of intermittency C1 has been also estimated. In the (H1,C1) phase diagram, the currency exchange rates are dispersed in a wide region around the Brownian motion value (H1=0.5,C1=0) and have a significantly intermittent component (C1≠0).

Empirical Tests of the Assumptions Underlying Models for Foreign Exchange Rates.

DTIC Science & Technology

1984-03-01

Research Report COs 481 EMPIRICAL TESTS OF THE ASSUMPTIO:IS UNDERLYING MODELS FOR FOREIGN EXCHANGE RATES by P. Brockett B. Golany 00 00 CENTER FOR...Research Report CCS 481 EMPIRICAL TESTS OF THE ASSUMPTIONS UNDERLYING MODELS FOR FOREIGN EXCHANGE RATES by P. Brockett B. Golany March 1984...applying these tests to the U.S. dollar to Japanese Yen foreign exchange rates . Conclusions and discussion is given in section VI. 1The previous authors

Vimentin filament precursors exchange subunits in an ATP-dependent manner

PubMed Central

Robert, Amélie; Rossow, Molly J.; Hookway, Caroline; Adam, Stephen A.; Gelfand, Vladimir I.

2015-01-01

Intermediate filaments (IFs) are a component of the cytoskeleton capable of profound reorganization in response to specific physiological situations, such as differentiation, cell division, and motility. Various mechanisms were proposed to be responsible for this plasticity depending on the type of IF polymer and the biological context. For example, recent studies suggest that mature vimentin IFs (VIFs) undergo rearrangement by severing and reannealing, but direct subunit exchange within the filament plays little role in filament dynamics at steady state. Here, we studied the dynamics of subunit exchange in VIF precursors, called unit-length filaments (ULFs), formed by the lateral association of eight vimentin tetramers. To block vimentin assembly at the ULF stage, we used the Y117L vimentin mutant (vimentinY117L). By tagging vimentinY117L with a photoconvertible protein mEos3.2 and photoconverting ULFs in a limited area of the cytoplasm, we found that ULFs, unlike mature filaments, were highly dynamic. Subunit exchange among ULFs occurred within seconds and was limited by the diffusion of soluble subunits in the cytoplasm rather than by the association and dissociation of subunits from ULFs. Our data demonstrate that cells expressing vimentinY117L contained a large pool of soluble vimentin tetramers that was in rapid equilibrium with ULFs. Furthermore, vimentin exchange in ULFs required ATP, and ATP depletion caused a dramatic reduction of the soluble tetramer pool. We believe that the dynamic exchange of subunits plays a role in the regulation of ULF assembly and the maintenance of a soluble vimentin pool during the reorganization of filament networks. PMID:26109569

CONTRIBUTIONS OF CHEMICAL EXCHANGE TO T1ρ DISPERSION IN A TISSUE MODEL

PubMed Central

Cobb, Jared G.; Xie, Jingping; Gore, John C.

2015-01-01

Variations in T1ρ with locking-field strength (T1ρ dispersion) may be used to estimate proton exchange rates. We developed a novel approach utilizing the second derivative of the dispersion curve to measure exchange in a model system of cross-linked polyacrylamide gels. These gels were varied in relative composition of co-monomers, increasing stiffness, and in pH, modifying exchange rates. MR images were recorded with a spin-locking sequence as described by Sepponen et al. These measurements were fit to a mono-exponential decay function yielding values for T1ρ at each locking-field measured. These values were then fit to a model by Chopra et al. for estimating exchange rates. For low stiffness gels, the calculated exchange values increased by a factor of 4 as pH increased, consistent with chemical exchange being the dominant contributor to T1ρ dispersion. Interestingly, calculated chemical exchange rates also increased with stiffness, likely due to modified side-chain exchange kinetics as the composition varied. This paper demonstrates a new method to assess the structural and chemical effects on T1ρ relaxation dispersion with a suitable model. These phenomena may be exploited in an imaging context to emphasize the presence of nuclei of specific exchange rates, rather than chemical shifts. PMID:21590720

78 FR 15777 - Self-Regulatory Organizations; EDGA Exchange, Inc.; Notice of Filing and Immediate Effectiveness...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-03-12

... equitable because these rates represent a blended or hybrid rate between the rates the Exchange assesses for... traditional Non-Displayed Order, which is hidden on the order book. The Exchange notes that its proposal...

Gas exchange and hydraulics in seedlings of Hevea brasiliensis during water stress and recovery.

PubMed

Chen, Jun-Wen; Zhang, Qiang; Li, Xiao-Shuang; Cao, Kun-Fang

2010-07-01

The response of plants to drought has received significant attention, but far less attention has been given to the dynamic response of plants during recovery from drought. Photosynthetic performance and hydraulic capacity were monitored in seedlings of Hevea brasiliensis under water stress and during recovery following rewatering. Leaf water relation, gas exchange rate and hydraulic conductivity decreased gradually after water stress fell below a threshold, whereas instantaneous water use efficiency and osmolytes increased significantly. After 5 days of rewatering, leaf water relation, maximum stomatal conductance (g(s-max)) and plant hydraulic conductivity had recovered to the control levels except for sapwood area-specific hydraulic conductivity, photosynthetic assimilation rate and osmolytes. During the phase of water stress, stomata were almost completely closed before water transport efficiency decreased substantially, and moreover, the leaf hydraulic pathway was more vulnerable to water stress-induced embolism than the stem hydraulic pathway. Meanwhile, g(s-max) was linearly correlated with hydraulic capacity when water stress exceeded a threshold. In addition, a positive relationship was shown to occur between the recovery of g(s-max) and of hydraulic capacity during the phase of rewatering. Our results suggest (i) that stomatal closure effectively reduces the risk of xylem dysfunction in water-stressed plants at the cost of gas exchange, (ii) that the leaf functions as a safety valve to protect the hydraulic pathway from water stress-induced dysfunction to a larger extent than does the stem and (iii) that the full drought recovery of gas exchange is restricted by not only hydraulic factors but also non-hydraulic factors.

Hydrogen storage systems based on magnesium hydride: from laboratory tests to fuel cell integration

NASA Astrophysics Data System (ADS)

de Rango, P.; Marty, P.; Fruchart, D.

2016-02-01

The paper reviews the state of the art of hydrogen storage systems based on magnesium hydride, emphasizing the role of thermal management, whose effectiveness depends on the effective thermal conductivity of the hydride, but also depends of other limiting factors such as wall contact resistance and convective exchanges with the heat transfer fluid. For daily cycles, the use of phase change material to store the heat of reaction appears to be the most effective solution. The integration with fuel cells (1 kWe proton exchange membrane fuel cell and solid oxide fuel cell) highlights the dynamic behaviour of these systems, which is related to the thermodynamic properties of MgH2. This allows for "self-adaptive" systems that do not require control of the hydrogen flow rate at the inlet of the fuel cell.

Hydrogen/deuterium exchange studies of native rabbit MM-CK dynamics.

PubMed

Mazon, Hortense; Marcillat, Olivier; Forest, Eric; Vial, Christian

2004-02-01

Creatine kinase (CK) isoenzymes catalyse the reversible transfer of a phosphoryl group from ATP onto creatine. This reaction plays a very important role in the regulation of intracellular ATP concentrations in excitable tissues. CK isoenzymes are highly resistant to proteases in native conditions. To appreciate localized backbone dynamics, kinetics of amide hydrogen exchange with deuterium was measured by pulse-labeling the dimeric cytosolic muscle CK isoenzyme. Upon exchange, the protein was digested with pepsin, and the deuterium content of the resulting peptides was determined by liquid chromatography coupled to mass spectrometry (MS). The deuteration kinetics of 47 peptides identified by MS/MS and covering 96% of the CK backbone were analyzed. Four deuteration patterns have been recognized: The less deuterated peptides are located in the saddle-shaped core of CK, whereas most of the highly deuterated peptides are close to the surface and located around the entrance to the active site. Their exchange kinetics are discussed by comparison with the known secondary and tertiary structures of CK with the goal to reveal the conformational dynamics of the protein. Some of the observed dynamic motions may be linked to the conformational changes associated with substrate binding and catalytic mechanism.

Foreign currency rate forecasting using neural networks

NASA Astrophysics Data System (ADS)

Pandya, Abhijit S.; Kondo, Tadashi; Talati, Amit; Jayadevappa, Suryaprasad

2000-03-01

Neural networks are increasingly being used as a forecasting tool in many forecasting problems. This paper discusses the application of neural networks in predicting daily foreign exchange rates between the USD, GBP as well as DEM. We approach the problem from a time-series analysis framework - where future exchange rates are forecasted solely using past exchange rates. This relies on the belief that the past prices and future prices are very close related, and interdependent. We present the result of training a neural network with historical USD-GBP data. The methodology used in explained, as well as the training process. We discuss the selection of inputs to the network, and present a comparison of using the actual exchange rates and the exchange rate differences as inputs. Price and rate differences are the preferred way of training neural network in financial applications. Results of both approaches are present together for comparison. We show that the network is able to learn the trends in the exchange rate movements correctly, and present the results of the prediction over several periods of time.

Structural and functional aspects of hetero-oligomers formed by the small heat shock proteins αB-crystallin and HSP27.

PubMed

Aquilina, J Andrew; Shrestha, Sudichhya; Morris, Amie M; Ecroyd, Heath

2013-05-10

αB-crystallin and HSP27 are mammalian intracellular small heat shock proteins. These proteins exchange subunits in a rapid and temperature-dependent manner. This facile subunit exchange suggests that differential expression could be used by the cell to regulate the response to stress. A robust technique defines parameters for the dynamic interaction between the major mammalian small heat shock proteins. Small heat shock proteins (sHSPs) exist as large polydisperse species in which there is constant dynamic subunit exchange between oligomeric and dissociated forms. Their primary role in vivo is to bind destabilized proteins and prevent their misfolding and aggregation. αB-Crystallin (αB) and HSP27 are the two most widely distributed and most studied sHSPs in the human body. They are coexpressed in different tissues, where they are known to associate with each other to form hetero-oligomeric complexes. In this study, we aimed to determine how these two sHSPs interact to form hetero-oligomers in vitro and whether, by doing so, there is an increase in their chaperone activity and stability compared with their homo-oligomeric forms. Our results demonstrate that HSP27 and αB formed polydisperse hetero-oligomers in vitro, which had an average molecular mass that was intermediate of each of the homo-oligomers and which were more thermostable than αB, but less so than HSP27. The hetero-oligomer chaperone function was found to be equivalent to that of αB, with each being significantly better in preventing the amorphous aggregation of α-lactalbumin and the amyloid fibril formation of α-synuclein in comparison with HSP27. Using mass spectrometry to monitor subunit exchange over time, we found that HSP27 and αB exchanged subunits 23% faster than the reported rate for HSP27 and αA and almost twice that for αA and αB. This represents the first quantitative evaluation of αB/HSP27 subunit exchange, and the results are discussed in the broader context of regulation of function and cellular proteostasis.

Structure and water exchange dynamics of hydrated oxo halo ions in aqueous solution using QMCF MD simulation, large angle X-ray scattering and EXAFS.

PubMed

Eklund, Lars; Hofer, Tomas S; Persson, Ingmar

2015-01-28

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) has been applied in conjunction with experimental large angle X-ray scattering (LAXS) and EXAFS measurements to study structure and dynamics of the hydrated oxo chloro anions chlorite, ClO2(-), chlorate, ClO3(-), and perchlorate, ClO4(-). In addition, the structures of the hydrated hypochlorite, ClO(-), bromate, BrO3(-), iodate, IO3(-) and metaperiodate, IO4(-), ions have been determined in aqueous solution by means of LAXS. The structures of the bromate, metaperiodate, and orthoperiodate, H2IO6(3-), ions have been determined by EXAFS as solid sodium salts and in aqueous solution as well. The results show clearly that the only form of periodate present in aqueous solution is metaperiodate. The Cl-O bond distances in the hydrated oxo chloro anions as determined by LAXS and obtained in the QMCF MD simulations are in excellent agreement, being 0.01-0.02 Å longer than in solid anhydrous salts due to hydration through hydrogen bonding to water molecules. The oxo halo anions, all with unit negative charge, have low charge density making them typical structure breakers, thus the hydrogen bonds formed to the hydrating water molecules are weaker and more short-lived than those between water molecules in pure water. The water exchange mechanism of the oxo chloro anions resembles those of the oxo sulfur anions with a direct exchange at the oxygen atoms for perchlorate and sulfate. The water exchange rate for the perchlorate ion is significantly faster, τ0.5 = 1.4 ps, compared to the hydrated sulfate ion and pure water, τ0.5 = 2.6 and 1.7 ps, respectively. The angular radial distribution functions show that the chlorate and sulfite ions have a more complex water exchange mechanism. As the chlorite and chlorate ions are more weakly hydrated than the sulfite ion the spatial occupancy is less well-defined and it is not possible to follow any well-defined migration pattern as it is difficult to distinguish between hydrating water molecules and bulk water in the region close to the ions.

Structure and water exchange dynamics of hydrated oxo halo ions in aqueous solution using QMCF MD simulation, large angle X-ray scattering and EXAFS

PubMed Central

Eklund, Lars; Hofer, Tomas S.

2014-01-01

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) has been applied in conjunction with experimental large angle X-ray scattering (LAXS) and EXAFS measurements to study structure and dynamics of the hydrated oxo chloro anions chlorite, ClO2−, chlorate, ClO3−, and perchlorate, ClO4−. In addition, the structures of the hydrated hypochlorite, ClO−, bromate, BrO3−, iodate, IO3− and metaperiodate, IO4−, ions have been determined in aqueous solution by means of LAXS. The structures of the bromate, metaperiodate, and orthoperiodate, H2IO63−, ions have been determined by EXAFS as solid sodium salts and in aqueous solution as well. The results show clearly that the only form of periodate present in aqueous solution is metaperiodate. The Cl-O bond distances in the hydrated oxo chloro anions as determined by LAXS and obtained in the QMCF MD simulations are in excellent agreement, being 0.01–0.02 Å longer than in solid anhydrous salts due to hydration through hydrogen bonding to water molecules. The oxo halo anions, all with unit negative charge, have low charge density making them typical structure breakers, thus the hydrogen bonds formed to the hydrating water molecules are weaker and more short-lived than those between water molecules in pure water. The water exchange mechanism of the oxo chloro anions resembles those of the oxo sulfur anions with a direct exchange at the oxygen atoms for perchlorate and sulfate. The water exchange rate for the perchlorate ion is significantly faster, τ0.5=1.4 ps, compared to the hydrated sulfate ion and pure water, τ0.5=2.6 and 1.7 ps, respectively. The angular radial distribution functions show that the chlorate and sulfite ions have a more complex water exchange mechanism. As the chlorite and chlorate ions are more weakly hydrated than the sulfite ion the spatial occupancy is less well-defined and it is not possible to follow any well-defined migration pattern as it is difficult to distinguish between hydrating water molecules and bulk water in the region close to the ions. PMID:25473816

Structure and water exchange dynamics of hydrated oxo halo ions in aqueous solution using QMCF MD simulation, large angle X-ray scattering and EXAFS

DOE PAGES

Eklund, Lars; Hofer, Tomas S.; Persson, Ingmar

2014-11-26

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) has been applied in conjunction with experimental large angle X-ray scattering (LAXS) and EXAFS measurements to study structure and dynamics of the hydrated oxo chloro anions chlorite, ClO 2 –, chlorate, ClO 3 –, and perchlorate, ClO 4 –. In addition, the structures of the hydrated hypochlorite, ClO –, bromate, BrO 3 –, iodate, IO 3 – and metaperiodate, IO 4 –, ions have been determined in aqueous solution by means of LAXS. The structures of the bromate, metaperiodate, and orthoperiodate, H 2IO 6 3–, ions have been determinedmore » by EXAFS as solid sodium salts and in aqueous solution as well. The results show clearly that the only form of periodate present in aqueous solution is metaperiodate. The Cl–O bond distances in the hydrated oxo chloro anions as determined by LAXS and obtained in the QMCF MD simulations are in excellent agreement, being 0.01–0.02 Å longer than in solid anhydrous salts due to hydration through hydrogen bonding to water molecules. The oxo halo anions, all with unit negative charge, have low charge density making them typical structure breakers, thus the hydrogen bonds formed to the hydrating water molecules are weaker and more short-lived than those between water molecules in pure water. The water exchange mechanism of the oxo chloro anions resembles those of the oxo sulfur anions with a direct exchange at the oxygen atoms for perchlorate and sulfate. Here, the water exchange rate for the perchlorate ion is significantly faster, τ 0.5 = 1.4 ps, compared to the hydrated sulfate ion and pure water, τ 0.5 = 2.6 and 1.7 ps, respectively. The angular radial distribution functions show that the chlorate and sulfite ions have a more complex water exchange mechanism. As the chlorite and chlorate ions are more weakly hydrated than the sulfite ion the spatial occupancy is less well-defined and it is not possible to follow any well-defined migration pattern as it is difficult to distinguish between hydrating water molecules and bulk water in the region close to the ions.« less

State politics and the creation of health insurance exchanges.

PubMed

Jones, David K; Greer, Scott L

2013-08-01

Health insurance exchanges are a key component of the Affordable Care Act. Each exchange faces the challenge of minimizing friction with existing policies, coordinating churn between programs, and maximizing take-up. State-run exchanges would likely be better positioned to address these issues than a federally run exchange, yet only one third of states chose this path. Policymakers must ensure that their exchange-whether state or federally run-succeeds. Whether this happens will greatly depend on the political dynamics in each state.

Sterility maintenance study: Dynamic evaluation of sterilized rigid containers and wrapped instrument trays to prevent bacterial ingress.

PubMed

Shaffer, Harry L; Harnish, Delbert A; McDonald, Michael; Vernon, Reid A; Heimbuch, Brian K

2015-12-01

Sterilized packaging systems are designed to maintain the sterility of surgical instruments and devices from the time of sterilization until use. This study evaluated the effectiveness of rigid containers versus wrapped instrument trays, sterilized using North American sterilization protocols, to maintain a sterile internal environment poststerilization when challenged with aerosolized bacteria under dynamic environmental conditions. Using a custom aerosol chamber, 111 rigid containers of various durations of use (unused, used <5 years, used 5-9 years) and 161 wrapped trays using 3 grades of sterilization wrap were challenged with ~10(2) colony-forming units per liter of air containing aerosolized Micrococcus luteus with a count median particle size of 1 μm, while simultaneously experiencing air volume exchanges due to vacuum cycles-two 1-psi cycles, three 0.7-psi cycles, and three 0.4-psi cycles-to simulate air exchange events occurring during the sterilization, transportation, and storage of sterilized instrument trays in health care facilities. Of 111 rigid containers tested, 97 (87%) demonstrated bacterial ingress into the container. Of 161 wrapped trays, 0 (0%) demonstrated bacterial ingress into the tray. Contamination rates of rigid containers increased significantly with increasing duration of use. In this study using a dynamic bacterial aerosol challenge, sterilized wrapped trays demonstrated significantly greater protection than sterilized rigid containers against the ingress of airborne bacteria. Copyright © 2015. Published by Elsevier Inc.

Intramolecular and Lattice Dynamics in V6-nIVVnV O7(OCH3)12 Crystal

NASA Astrophysics Data System (ADS)

Yablokov, Yu. V.; Augustyniak-Jabłokow, M. A.; Borshch, S.; Daniel, C.; Hartl, H.

2006-08-01

Multi-nuclear mixed-valence clusters V4IVV2VO7(OCH3)12 were studied by X-band EPR in the temperature range 4.2-300 K. An isotropic exchange interactions between four VIV ions with individual spin Si=1/2 determine the energy levels structure of the compound with the total spin states S=0, 1, and 2, which are doubled and split due to the extra electron transfer. The spin-Hamiltonian approach was used for the analysis of the temperature dependences of the EPR spectra parameters and the cluster dynamics. Two types of the electron transfer are assumed: the single jump transfer leading to the splitting of the total spin states by intervals comparable in magnitude with the exchange parameter J≈100-150cm-1 and the double jump one resulting in dynamics. The dependence of the transition ratesνtr on the energy of the total spin states was observed. In particular, in the range 300-220 K the νtr ≈0.7×1010 cm-1 and below 180 K the νtr≈1×1010 cm-1 was estimated. The g-factors of the spin states were shown to depend on the values of the intermediate spins. A phase transition in the T-range 210-180 K leading to the change in the initial VIV ions localization was discovered.

Modeling volatility using state space models.

PubMed

Timmer, J; Weigend, A S

1997-08-01

In time series problems, noise can be divided into two categories: dynamic noise which drives the process, and observational noise which is added in the measurement process, but does not influence future values of the system. In this framework, we show that empirical volatilities (the squared relative returns of prices) exhibit a significant amount of observational noise. To model and predict their time evolution adequately, we estimate state space models that explicitly include observational noise. We obtain relaxation times for shocks in the logarithm of volatility ranging from three weeks (for foreign exchange) to three to five months (for stock indices). In most cases, a two-dimensional hidden state is required to yield residuals that are consistent with white noise. We compare these results with ordinary autoregressive models (without a hidden state) and find that autoregressive models underestimate the relaxation times by about two orders of magnitude since they do not distinguish between observational and dynamic noise. This new interpretation of the dynamics of volatility in terms of relaxators in a state space model carries over to stochastic volatility models and to GARCH models, and is useful for several problems in finance, including risk management and the pricing of derivative securities. Data sets used: Olsen & Associates high frequency DEM/USD foreign exchange rates (8 years). Nikkei 225 index (40 years). Dow Jones Industrial Average (25 years).

Oil price and exchange rate co-movements in Asian countries: Detrended cross-correlation approach

NASA Astrophysics Data System (ADS)

Hussain, Muntazir; Zebende, Gilney Figueira; Bashir, Usman; Donghong, Ding

2017-01-01

Most empirical literature investigates the relation between oil prices and exchange rate through different models. These models measure this relationship on two time scales (long and short terms), and often fail to observe the co-movement of these variables at different time scales. We apply a detrended cross-correlation approach (DCCA) to investigate the co-movements of the oil price and exchange rate in 12 Asian countries. This model determines the co-movements of oil price and exchange rate at different time scale. The exchange rate and oil price time series indicate unit root problem. Their correlation and cross-correlation are very difficult to measure. The result becomes spurious when periodic trend or unit root problem occurs in these time series. This approach measures the possible cross-correlation at different time scale and controlling the unit root problem. Our empirical results support the co-movements of oil prices and exchange rate. Our results support a weak negative cross-correlation between oil price and exchange rate for most Asian countries included in our sample. The results have important monetary, fiscal, inflationary, and trade policy implications for these countries.

Stationarity test with a direct test for heteroskedasticity in exchange rate forecasting models

NASA Astrophysics Data System (ADS)

Khin, Aye Aye; Chau, Wong Hong; Seong, Lim Chee; Bin, Raymond Ling Leh; Teng, Kevin Low Lock

2017-05-01

Global economic has been decreasing in the recent years, manifested by the greater exchange rates volatility on international commodity market. This study attempts to analyze some prominent exchange rate forecasting models on Malaysian commodity trading: univariate ARIMA, ARCH and GARCH models in conjunction with stationarity test on residual diagnosis direct testing of heteroskedasticity. All forecasting models utilized the monthly data from 1990 to 2015. Given a total of 312 observations, the data used to forecast both short-term and long-term exchange rate. The forecasting power statistics suggested that the forecasting performance of ARIMA (1, 1, 1) model is more efficient than the ARCH (1) and GARCH (1, 1) models. For ex-post forecast, exchange rate was increased from RM 3.50 per USD in January 2015 to RM 4.47 per USD in December 2015 based on the baseline data. For short-term ex-ante forecast, the analysis results indicate a decrease in exchange rate on 2016 June (RM 4.27 per USD) as compared with 2015 December. A more appropriate forecasting method of exchange rate is vital to aid the decision-making process and planning on the sustainable commodities' production in the world economy.

Critical Spin Superflow in a Spinor Bose-Einstein Condensate

NASA Astrophysics Data System (ADS)

Kim, Joon Hyun; Seo, Sang Won; Shin, Y.

2017-11-01

We investigate the critical dynamics of spin superflow in an easy-plane antiferromagnetic spinor Bose-Einstein condensate. Spin-dipole oscillations are induced in a trapped condensate by applying a linear magnetic field gradient and we observe that the damping rate increases rapidly as the field gradient increases above a certain critical value. The onset of dissipation is found to be associated with the generation of dark-bright solitons due to the modulation instability of the counterflow of two spin components. Spin turbulence emerges as the solitons decay because of their snake instability. We identify another critical point for spin superflow, in which transverse magnon excitations are dynamically generated via spin-exchanging collisions, which leads to the transient formation of axial polar spin domains.

Interactions Between Suspended Kaolinite Deposition and Hyporheic Exchange Flux Under Losing and Gaining Flow Conditions

NASA Astrophysics Data System (ADS)

Fox, Aryeh; Packman, Aaron I.; Boano, Fulvio; Phillips, Colin B.; Arnon, Shai

2018-05-01

Fine particle deposition and streambed clogging affect many ecological and biogeochemical processes, but little is known about the effects of groundwater flow into and out of rivers on clogging. We evaluated the effects of losing and gaining flow on the deposition of suspended kaolinite clay particles in a sand streambed and the resulting changes in rates and patterns of hyporheic exchange flux (HEF). Observations of clay deposition from the water column, clay accumulation in the streambed sediments, and water exchange with the bed demonstrated that clay deposition in the bed substantially reduced both HEF and the size of the hyporheic zone. Clay deposition and HEF were strongly coupled, leading to rapid clogging in areas of water and clay influx into the bed. Local clogging diverted exchanged water laterally, producing clay deposit layers that reduced vertical hyporheic flow and favored horizontal flow. Under gaining conditions, HEF was spatially constrained by upwelling water, which focused clay deposition in a small region on the upstream side of each bed form. Because the area of inflow into the bed was smallest under gaining conditions, local clogging required less clay mass under gaining conditions than neutral or losing conditions. These results indicate that losing and gaining flow conditions need to be considered in assessments of hyporheic exchange, fine particle dynamics in streams, and streambed clogging and restoration.

Sub-Ensemble Monitoring of DNA Strand Displacement Using Multiparameter Single-Molecule FRET.

PubMed

Baltierra-Jasso, Laura E; Morten, Michael J; Magennis, Steven W

2018-03-05

Non-enzymatic DNA strand displacement is an important mechanism in dynamic DNA nanotechnology. Here, we show that the large parameter space that is accessible by single-molecule FRET is ideal for the simultaneous monitoring of multiple reactants and products of DNA strand exchange reactions. We monitored the strand displacement from double-stranded DNA (dsDNA) by single-stranded DNA (ssDNA) at 37 °C; the data were modelled as a second-order reaction approaching equilibrium, with a rate constant of 10 m -1  s -1 . We also followed the displacement from a DNA three-way junction (3WJ) by ssDNA. The presence of three internal mismatched bases in the middle of the invading strand did not prevent displacement from the 3WJ, but reduced the second-order rate constant by about 50 %. We attribute strand exchange in the dsDNA and 3WJ to a zero-toehold pathway from the blunt-ended duplex arms. The single-molecule approach demonstrated here will be useful for studying complex DNA networks. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analyzing the Cross-Correlation Between Onshore and Offshore RMB Exchange Rates Based on Multifractal Detrended Cross-Correlation Analysis (MF-DCCA)

NASA Astrophysics Data System (ADS)

Xie, Chi; Zhou, Yingying; Wang, Gangjin; Yan, Xinguo

We use the multifractal detrended cross-correlation analysis (MF-DCCA) method to explore the multifractal behavior of the cross-correlation between exchange rates of onshore RMB (CNY) and offshore RMB (CNH) against US dollar (USD). The empirical data are daily prices of CNY/USD and CNH/USD from May 1, 2012 to February 29, 2016. The results demonstrate that: (i) the cross-correlation between CNY/USD and CNH/USD is persistent and its fluctuation is smaller when the order of fluctuation function is negative than that when the order is positive; (ii) the multifractal behavior of the cross-correlation between CNY/USD and CNH/USD is significant during the sample period; (iii) the dynamic Hurst exponents obtained by the rolling windows analysis show that the cross-correlation is stable when the global economic situation is good and volatile in bad situation; and (iv) the non-normal distribution of original data has a greater effect on the multifractality of the cross-correlation between CNY/USD and CNH/USD than the temporary correlation.

Regimes of heating and dynamical response in driven many-body localized systems

NASA Astrophysics Data System (ADS)

Gopalakrishnan, Sarang; Knap, Michael; Demler, Eugene

2016-09-01

We explore the response of many-body localized (MBL) systems to periodic driving of arbitrary amplitude, focusing on the rate at which they exchange energy with the drive. To this end, we introduce an infinite-temperature generalization of the effective "heating rate" in terms of the spread of a random walk in energy space. We compute this heating rate numerically and estimate it analytically in various regimes. When the drive amplitude is much smaller than the frequency, this effective heating rate is given by linear response theory with a coefficient that is proportional to the optical conductivity; in the opposite limit, the response is nonlinear and the heating rate is a nontrivial power law of time. We discuss the mechanisms underlying this crossover in the MBL phase. We comment on implications for the subdiffusive thermal phase near the MBL transition, and for response in imperfectly isolated MBL systems.

Application of Multiplexed Replica Exchange Molecular Dynamics to the UNRES Force Field: Tests with alpha and alpha+beta Proteins.

PubMed

Czaplewski, Cezary; Kalinowski, Sebastian; Liwo, Adam; Scheraga, Harold A

2009-03-10

The replica exchange (RE) method is increasingly used to improve sampling in molecular dynamics (MD) simulations of biomolecular systems. Recently, we implemented the united-residue UNRES force field for mesoscopic MD. Initial results from UNRES MD simulations show that we are able to simulate folding events that take place in a microsecond or even a millisecond time scale. To speed up the search further, we applied the multiplexing replica exchange molecular dynamics (MREMD) method. The multiplexed variant (MREMD) of the RE method, developed by Rhee and Pande, differs from the original RE method in that several trajectories are run at a given temperature. Each set of trajectories run at a different temperature constitutes a layer. Exchanges are attempted not only within a single layer but also between layers. The code has been parallelized and scales up to 4000 processors. We present a comparison of canonical MD, REMD, and MREMD simulations of protein folding with the UNRES force-field. We demonstrate that the multiplexed procedure increases the power of replica exchange MD considerably and convergence of the thermodynamic quantities is achieved much faster.

Application of Multiplexed Replica Exchange Molecular Dynamics to the UNRES Force Field: Tests with α and α+β Proteins

PubMed Central

Czaplewski, Cezary; Kalinowski, Sebastian; Liwo, Adam; Scheraga, Harold A.

2009-01-01

The replica exchange (RE) method is increasingly used to improve sampling in molecular dynamics (MD) simulations of biomolecular systems. Recently, we implemented the united-residue UNRES force field for mesoscopic MD. Initial results from UNRES MD simulations show that we are able to simulate folding events that take place in a microsecond or even a millisecond time scale. To speed up the search further, we applied the multiplexing replica exchange molecular dynamics (MREMD) method. The multiplexed variant (MREMD) of the RE method, developed by Rhee and Pande, differs from the original RE method in that several trajectories are run at a given temperature. Each set of trajectories run at a different temperature constitutes a layer. Exchanges are attempted not only within a single layer but also between layers. The code has been parallelized and scales up to 4000 processors. We present a comparison of canonical MD, REMD, and MREMD simulations of protein folding with the UNRES force-field. We demonstrate that the multiplexed procedure increases the power of replica exchange MD considerably and convergence of the thermodynamic quantities is achieved much faster. PMID:20161452

Flow-Induced New Channels of Energy Exchange in Multi-Scale Plasma Dynamics - Revisiting Perturbative Hybrid Kinetic-MHD Theory.

PubMed

Shiraishi, Junya; Miyato, Naoaki; Matsunaga, Go

2016-05-10

It is found that new channels of energy exchange between macro- and microscopic dynamics exist in plasmas. They are induced by macroscopic plasma flow. This finding is based on the kinetic-magnetohydrodynamic (MHD) theory, which analyses interaction between macroscopic (MHD-scale) motion and microscopic (particle-scale) dynamics. The kinetic-MHD theory is extended to include effects of macroscopic plasma flow self-consistently. The extension is realised by generalising an energy exchange term due to wave-particle resonance, denoted by δ WK. The first extension is generalisation of the particle's Lagrangian, and the second one stems from modification to the particle distribution function due to flow. These extensions lead to a generalised expression of δ WK, which affects the MHD stability of plasmas.

Energy exchange analysis in droplet dynamics via the Navier-Stokes-Cahn-Hilliard model

NASA Astrophysics Data System (ADS)

Espath, L. F. R.; Sarmiento, A. F.; Vignal, P.; Varga, B. O. N.; Cortes, A. M. A.; Dalcin, L.; Calo, V. M.

2016-06-01

We develop the energy budget equation of the coupled Navier-Stokes-Cahn-Hilliard (NSCH) system. We use the NSCH equations to model the dynamics of liquid droplets in a liquid continuum. Buoyancy effects are accounted for through the Boussinesq assumption. We physically interpret each quantity involved in the energy exchange to further insight into the model. Highly resolved simulations involving density-driven flows and merging of droplets allow us to analyze these energy budgets. In particular, we focus on the energy exchanges when droplets merge, and describe flow features relevant to this phenomenon. By comparing our numerical simulations to analytical predictions and experimental results available in the literature, we conclude that modeling droplet dynamics within the framework of NSCH equations is a sensible approach worth further research.

Non-equilibrium magnetic interactions in strongly correlated systems

NASA Astrophysics Data System (ADS)

Secchi, A.; Brener, S.; Lichtenstein, A. I.; Katsnelson, M. I.

2013-06-01

We formulate a low-energy theory for the magnetic interactions between electrons in the multi-band Hubbard model under non-equilibrium conditions determined by an external time-dependent electric field which simulates laser-induced spin dynamics. We derive expressions for dynamical exchange parameters in terms of non-equilibrium electronic Green functions and self-energies, which can be computed, e.g., with the methods of time-dependent dynamical mean-field theory. Moreover, we find that a correct description of the system requires, in addition to exchange, a new kind of magnetic interaction, that we name twist exchange, which formally resembles Dzyaloshinskii-Moriya coupling, but is not due to spin-orbit, and is actually due to an effective three-spin interaction. Our theory allows the evaluation of the related time-dependent parameters as well.

Assessing the Efficacy of Adjustable Moving Averages Using ASEAN-5 Currencies

PubMed Central

2016-01-01

The objective of this research is to examine the trends in the exchange rate markets of the ASEAN-5 countries (Indonesia (IDR), Malaysia (MYR), the Philippines (PHP), Singapore (SGD), and Thailand (THB)) through the application of dynamic moving average trading systems. This research offers evidence of the usefulness of the time-varying volatility technical analysis indicator, Adjustable Moving Average (AMA′) in deciphering trends in these ASEAN-5 exchange rate markets. This time-varying volatility factor, referred to as the Efficacy Ratio in this paper, is embedded in AMA′. The Efficacy Ratio adjusts the AMA′ to the prevailing market conditions by avoiding whipsaws (losses due, in part, to acting on wrong trading signals, which generally occur when there is no general direction in the market) in range trading and by entering early into new trends in trend trading. The efficacy of AMA′ is assessed against other popular moving-average rules. Based on the January 2005 to December 2014 dataset, our findings show that the moving averages and AMA′ are superior to the passive buy-and-hold strategy. Specifically, AMA′ outperforms the other models for the United States Dollar against PHP (USD/PHP) and USD/THB currency pairs. The results show that different length moving averages perform better in different periods for the five currencies. This is consistent with our hypothesis that a dynamic adjustable technical indicator is needed to cater for different periods in different markets. PMID:27574972

Stochastic dynamics and non-equilibrium thermodynamics of a bistable chemical system: the Schlögl model revisited.

PubMed

Vellela, Melissa; Qian, Hong

2009-10-06

Schlögl's model is the canonical example of a chemical reaction system that exhibits bistability. Because the biological examples of bistability and switching behaviour are increasingly numerous, this paper presents an integrated deterministic, stochastic and thermodynamic analysis of the model. After a brief review of the deterministic and stochastic modelling frameworks, the concepts of chemical and mathematical detailed balances are discussed and non-equilibrium conditions are shown to be necessary for bistability. Thermodynamic quantities such as the flux, chemical potential and entropy production rate are defined and compared across the two models. In the bistable region, the stochastic model exhibits an exchange of the global stability between the two stable states under changes in the pump parameters and volume size. The stochastic entropy production rate shows a sharp transition that mirrors this exchange. A new hybrid model that includes continuous diffusion and discrete jumps is suggested to deal with the multiscale dynamics of the bistable system. Accurate approximations of the exponentially small eigenvalue associated with the time scale of this switching and the full time-dependent solution are calculated using Matlab. A breakdown of previously known asymptotic approximations on small volume scales is observed through comparison with these and Monte Carlo results. Finally, in the appendix section is an illustration of how the diffusion approximation of the chemical master equation can fail to represent correctly the mesoscopically interesting steady-state behaviour of the system.

Hydro-geomorphic perturbations on the soil-atmosphere CO2 exchange: How (un)certain are our balances?

NASA Astrophysics Data System (ADS)

Dialynas, Yannis G.; Bras, Rafael L.; deB. Richter, Daniel

2017-02-01

Attempts to estimate the influence of erosion on the carbon (C) cycle are limited by difficulties in accounting for the fate of mobilized organic material and for the uncertainty associated with land management practices. This study proposes a method to quantify the uncertainty introduced by the influence of land management on soil organic C (SOC) generation and decomposition at eroding soils. The framework is implemented in tRIBS-ECO (Triangulated Irregular Network-based Real-time Integrated Basin Simulator-Erosion and Carbon Oxidation). tRIBS-ECO is a spatially and depth-explicit model of C dynamics coupled with a process-based hydro-geomorphic model. We assess the impact of soil erosion on the net soil-atmosphere CO2 exchange at the Calhoun Critical Zone Observatory, one of the most severely agriculturally eroded regions in the U.S. Measurements of SOC storage are used from different catena positions. We demonstrate that the spatiotemporal variations of land management practices introduce significant uncertainty in estimates of the erosion-induced CO2 exchange with the atmosphere. Observations and simulations suggest that a substantial portion of eroded organic material is buried in alluvial sediments at the study site. According to results, recent reforestation led to a partial decline in soil and SOC erosion rates. It is suggested that the representation of the fine spatiotemporal variability of the dynamics of eroded C is important in the computation of C budgets in regional and global scales.

All-atom molecular dynamics calculation study of entire poliovirus empty capsids in solution

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

Andoh, Y.; Yoshii, N.; Yamada, A.

2014-10-28

Small viruses that belong, for example, to the Picornaviridae, such as poliovirus and foot-and-mouth disease virus, consist simply of capsid proteins and a single-stranded RNA (ssRNA) genome. The capsids are quite stable in solution to protect the genome from the environment. Here, based on long-time and large-scale 6.5 × 10{sup 6} all-atom molecular dynamics calculations for the Mahoney strain of poliovirus, we show microscopic properties of the viral capsids at a molecular level. First, we found equilibrium rapid exchange of water molecules across the capsid. The exchange rate is so high that all water molecules inside the capsid (about 200 000)more » can leave the capsid and be replaced by water molecules from the outside in about 25 μs. This explains the capsid's tolerance to high pressures and deactivation by exsiccation. In contrast, the capsid did not exchange ions, at least within the present simulation time of 200 ns. This implies that the capsid can function, in principle, as a semipermeable membrane. We also found that, similar to the xylem of trees, the pressure of the solution inside the capsid without the genome was negative. This is caused by coulombic interaction of the solution inside the capsid with the capsid excess charges. The negative pressure may be compensated by positive osmotic pressure by the solution-soluble ssRNA and the counter ions introduced into it.« less

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

Almasbahi, M.S.

In a world of generalized floating exchange rates, it is not enough to solve the problem of exchange rate policy by determining whether to peg or float the currency under consideration. It is also necessary to choose to what major currency to peg. The main purpose of this study is to investigate and determine empirically the optimum currency peg for the Saudi riyal. To accomplish this goal, a simple conventional trade model, that includes variables found in many other studies of import and export demand, was used. In addition, an exchange rate term was added as a separate independent variablemore » in the import and export demand equations in order to assess the effect of exchange rate on the trade flows. The criteria for the optimal currency peg in this study were based on two factors. First, the error statistics for projected imports and exports using alternative exchange rate regimes. Second, variances of projected imports, exports and trade balance using alternative exchange rate regimes. The exchange rate has a significant impact on the Saudia Arabian trade flows which implies that changes in the riyals value affect the Saudi trade deficit. Moreover, the exchange rate has a more powerful effect on its aggregate imports than on the world demand for its exports. There is also a strong support for the hypothesis that the exchange rate affects the value of the Saudi bilateral trade with its five major trade partners. On the aggregate level, the SDR peg seems to be the best currency peg for the Saudi riyal since it provides the best prediction errors and the lowest variance for the trade balance. Finally, on the disaggregate level, the US dollar provides the best performance and yields the best results among all the six currency pegs considered in this study.« less

Canopy Dynamics in Nanoscale Ionic Materials Probed by NMR

NASA Astrophysics Data System (ADS)

Mirau, Peter

2013-03-01

Nanoscale ionic materials (NIMs) are hybrids prepared from ionically functionalized nanoparticles (NP) neutralized by oligomeric polymer counter-ions. NIMs are designed to behave as liquids under ambient conditions in the absence of solvent and have no volatile organic content, making them useful for a number of applications. We have used NMR relaxation and pulse-field gradient NMR to probe local and collective canopy dynamics in NIMs based on silica nanoparticles (NP), fullerols and proteins in order to understand the relationship between the core and canopy structure and the bulk properties. The NMR studies show that the canopy dynamics depend on the degree of neutralization, the canopy radius of gyration and molecular crowding at the ionically modified NP surface. The viscosity in NIMs can be directly controlled with the addition of ions that enhance the exchange rate for polymers at the NP surface. These results show that NIMs for many applications can be prepared by controlling the dynamics of the NP interface.

Finite-time singularities in the dynamics of Mexican financial crises

NASA Astrophysics Data System (ADS)

Alvarez-Ramirez, Jose; Ibarra-Valdez, Carlos

2004-01-01

Historically, symptoms of Mexican financial crises have been strongly reflected in the dynamics of the Mexican peso to the dollar exchange currency market. Specifically, in the Mexican financial crises during 1990's, the peso suffered significant depreciation processes, which has important impacts in the macro- and micro-economical environment. In this paper, it is shown that the peso depreciation growth was greater than an exponential and that these growth rates are compatible with a spontaneous singularity occurring at a critical time, which signals an abrupt transition to new dynamical conditions. As in the major 1990's financial crisis in 1994-1995, some control actions (e.g., increasing the USA dollar supply) are commonly taken to decelerate the degree of abruptness of peso depreciation. Implications of these control actions on the crisis dynamics are discussed. Interestingly, by means of a simple model, it is demonstrated that the time at which the control actions begin to apply is critical to moderate the adverse effects of the financial crisis.

Dynamic Coupling and Allosteric Networks in the α Subunit of Heterotrimeric G Proteins.

PubMed

Yao, Xin-Qiu; Malik, Rabia U; Griggs, Nicholas W; Skjærven, Lars; Traynor, John R; Sivaramakrishnan, Sivaraj; Grant, Barry J

2016-02-26

G protein α subunits cycle between active and inactive conformations to regulate a multitude of intracellular signaling cascades. Important structural transitions occurring during this cycle have been characterized from extensive crystallographic studies. However, the link between observed conformations and the allosteric regulation of binding events at distal sites critical for signaling through G proteins remain unclear. Here we describe molecular dynamics simulations, bioinformatics analysis, and experimental mutagenesis that identifies residues involved in mediating the allosteric coupling of receptor, nucleotide, and helical domain interfaces of Gαi. Most notably, we predict and characterize novel allosteric decoupling mutants, which display enhanced helical domain opening, increased rates of nucleotide exchange, and constitutive activity in the absence of receptor activation. Collectively, our results provide a framework for explaining how binding events and mutations can alter internal dynamic couplings critical for G protein function. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Dynamic Business Networks: A Headache for Sustainable Systems Interoperability

NASA Astrophysics Data System (ADS)

Agostinho, Carlos; Jardim-Goncalves, Ricardo

Collaborative networked environments emerged with the spread of the internet, contributing to overcome past communication barriers, and identifying interoperability as an essential property. When achieved seamlessly, efficiency is increased in the entire product life cycle. Nowadays, most organizations try to attain interoperability by establishing peer-to-peer mappings with the different partners, or in optimized networks, by using international standard models as the core for information exchange. In current industrial practice, mappings are only defined once, and the morphisms that represent them, are hardcoded in the enterprise systems. This solution has been effective for static environments, where enterprise and product models are valid for decades. However, with an increasingly complex and dynamic global market, models change frequently to answer new customer requirements. This paper draws concepts from the complex systems science and proposes a framework for sustainable systems interoperability in dynamic networks, enabling different organizations to evolve at their own rate.

Stellar-mass black holes in young massive and open stellar clusters and their role in gravitational-wave generation - II

NASA Astrophysics Data System (ADS)

Banerjee, Sambaran

2018-01-01

The study of stellar-remnant black holes (BH) in dense stellar clusters is now in the spotlight, especially due to their intrinsic ability to form binary black holes (BBH) through dynamical encounters, which potentially coalesce via gravitational-wave (GW) radiation. In this work, which is a continuation from a recent study (Paper I), additional models of compact stellar clusters with initial masses ≲ 105 M⊙ and also those with small fractions of primordial binaries (≲ 10 per cent) are evolved for long term, applying the direct N-body approach, assuming state-of-the-art stellar-wind and remnant-formation prescriptions. That way, a substantially broader range of computed models than that in Paper I is achieved. As in Paper I, the general-relativistic BBH mergers continue to be mostly mediated by triples that are bound to the clusters rather than happen among the ejected BBHs. In fact, the number of such in situ BBH mergers, per cluster, tends to increase significantly with the introduction of a small population of primordial binaries. Despite the presence of massive primordial binaries, the merging BBHs, especially the in situ ones, are found to be exclusively dynamically assembled and hence would be spin-orbit misaligned. The BBHs typically traverse through both the LISA's and the LIGO's detection bands, being audible to both instruments. The 'dynamical heating' of the BHs keeps the electron-capture-supernova (ECS) neutron stars (NS) from effectively mass segregating and participating in exchange interactions; the dynamically active BHs would also exchange into any NS binary within ≲1 Gyr. Such young massive and open clusters have the potential to contribute to the dynamical BBH merger detection rate to a similar extent as their more massive globular-cluster counterparts.

All-optical measurement of interlayer exchange coupling in Fe/Pt/FePt thin films

NASA Astrophysics Data System (ADS)

Berk, C.; Ganss, F.; Jaris, M.; Albrecht, M.; Schmidt, H.

2018-01-01

Time Resolved Magneto Optic Kerr Effect spectroscopy was used to all-optically study the dynamics in exchange coupled Fe(10 nm)/Pt(x = 0-5 nm)/FePt (10 nm) thin films. As the Pt spacer decreases, the effective magnetization of the layers is seen to evolve towards the strong coupling limit where the two films can be described by a single effective magnetization. The coupling begins at x = 1.5 nm and reaches a maximum exchange coupling constant of 2.89 erg/cm2 at x = 0 nm. The films are ferromagnetically coupled at all Pt thicknesses in the exchange coupled regime (x ≤ 1.5 nm). A procedure for extracting the interlayer exchange constant by measuring the magnetic precession frequencies at multiple applied fields and angles is outlined. The dynamics are well reproduced using micromagnetic simulations.

Spin-wave dynamics and exchange interactions in multiferroic NdFe3(BO3)4 explored by inelastic neutron scattering

NASA Astrophysics Data System (ADS)

Golosovsky, I. V.; Ovsyanikov, A. K.; Aristov, D. N.; Matveeva, P. G.; Mukhin, A. A.; Boehm, M.; Regnault, L.-P.; Bezmaternykh, L. N.

2018-04-01

Magnetic excitations and exchange interactions in multiferroic NdFe3(BO3)4 were studied by inelastic neutron scattering in the phase with commensurate antiferromagnetic structure. The observed spectra were analyzed in the frame of the linear spin-wave theory. It was shown that only the model, which includes the exchange interactions within eight coordination spheres, describes satisfactorily all observed dispersion curves. The calculation showed that the spin-wave dynamics is governed by the strongest antiferromagnetic intra-chain interaction and three almost the same inter-chain interactions. Other interactions, including ferromagnetic exchange, appeared to be insignificant. The overall energy balance of the antiferromagnetic inter-chain exchange interactions, which couple the moments from the adjacent ferromagnetic layers as well as within a layer, stabilizes ferromagnetic arrangement in the latter. It demonstrates that the pathway geometry plays a crucial role in forming of the magnetic structure.

NASA geometry data exchange specification for computational fluid dynamics (NASA IGES)

NASA Technical Reports Server (NTRS)

Blake, Matthew W.; Kerr, Patricia A.; Thorp, Scott A.; Jou, Jin J.

1994-01-01

This document specifies a subset of an existing product data exchange specification that is widely used in industry and government. The existing document is called the Initial Graphics Exchange Specification. This document, a subset of IGES, is intended for engineers analyzing product performance using tools such as computational fluid dynamics (CFD) software. This document specifies how to define mathematically and exchange the geometric model of an object. The geometry is represented utilizing nonuniform rational B-splines (NURBS) curves and surfaces. Only surface models are represented; no solid model representation is included. This specification does not include most of the other types of product information available in IGES (e.g., no material properties or surface finish properties) and does not provide all the specific file format details of IGES. The data exchange protocol specified in this document is fully conforming to the American National Standard (ANSI) IGES 5.2.

Free float and stochastic volatility: the experience of a small open economy

NASA Astrophysics Data System (ADS)

Selçuk, Faruk

2004-11-01

Following a dramatic collapse of a fixed exchange rate based inflation stabilization program, Turkey moved into a free floating exchange rate system in February 2001. In this paper, an asymmetric stochastic volatility model of the foreign exchange rate in Turkey is estimated for the floating period. It is shown that there is a positive relation between the exchange return and its volatility. Particularly, an increase in the return at time t results in an increase in volatility at time t+1. However, the effect is asymmetric: a decrease in the exchange rate return at time t causes a relatively less decrease in volatility at time t+1. The results imply that a central bank with a volatility smoothing policy would be biased in viewing the shocks to the exchange rate in favor of appreciation. The bias would increase if the bank is also following an inflation targeting policy.

Spin and orbital exchange interactions from Dynamical Mean Field Theory

NASA Astrophysics Data System (ADS)

Secchi, A.; Lichtenstein, A. I.; Katsnelson, M. I.

2016-02-01

We derive a set of equations expressing the parameters of the magnetic interactions characterizing a strongly correlated electronic system in terms of single-electron Green's functions and self-energies. This allows to establish a mapping between the initial electronic system and a spin model including up to quadratic interactions between the effective spins, with a general interaction (exchange) tensor that accounts for anisotropic exchange, Dzyaloshinskii-Moriya interaction and other symmetric terms such as dipole-dipole interaction. We present the formulas in a format that can be used for computations via Dynamical Mean Field Theory algorithms.

Geometric phase effects in ultracold hydrogen exchange reaction

DOE PAGES

Hazra, Jisha; Kendrick, Brian K.; Balakrishnan, Naduvalath

2016-10-14

The role of the geometric phase effect on chemical reaction dynamics is explored by examining the hydrogen exchange process in the fundamental H+HD reaction. Results are presented for vibrationally excited HD molecules in the v = 4 vibrational level and for collision energies ranging from 1 μK to 100 K. It is found that, for collision energies below 3 K, inclusion of the geometric phase leads to dramatic enhancement or suppression of the reaction rates depending on the final quantum state of the HD molecule. The effect was found to be the most prominent for rotationally resolved integral and differential cross sections but it persists to a lesser extent in the vibrationally resolved and total reaction rate coefficients. However, no significant GP effect is present in the reactive channel leading to the D+H 2 product or in the D+H 2more » $$(v=4,j=0)\\,\\to $$ HD+H reaction. A simple interference mechanism involving inelastic (nonreactive) and exchange scattering amplitudes is invoked to account for the observed GP effects. The computed results also reveal a shape resonance in the H+HD reaction near 1 K and the GP effect is found to influence the magnitude of the resonant part of the cross section. In conclusion, experimental detection of the resonance may allow a sensitive probe of the GP effect in the H+HD reaction.« less

Transport dynamics in a sheltered estuary and connecting tidal straits: SF6 tracer study in New York Harbor.

PubMed

Caplow, Theodore; Schlosser, Peter; Ho, David T; Santella, Nicholas

2003-11-15

In July 2002, approximately 0.9 mol of sulfur hexafluoride (SF6) was injected into Newark Bay, NJ, a 14 km2 estuary that forms part of New York Harbor, to investigate circulation, mixing, and the transport and fate of solutes. The SF6 tracer was observed over 11 consecutive days using a high-resolution measurement system. Total tracer mass in the sheltered waters declined quasiexponentially at a rate of 0.29 +/- 0.03 d(-1). Air-water gas exchange was estimated to account for 56% of tracer mass loss, upon the basis of wind speed/gas exchange parametrizations. Large-scale tidal transfer of solutes through the Kill van Kull strait (7 km long) caused net seaward flushing contrary to the apparent residual circulation. Seaward transport via the Arthur Kill strait (20 km long) appeared to depend on longitudinal dispersion, residual circulation, and freshwater discharge and was approximately 1 order of magnitude lower. The loss rate due to flushing alone was 0.13 +/- 0.02 d(-1), indicating a mean residence time for water and solutes in Newark Bay of approximately 8 days (without gas exchange). The experiment provides direct visualization of the transport of a released contaminant, and suggests a relationship between the length and configuration of tidal straits and related transport of solutes.

Submicrosecond phospholipid dynamics using a long-lived fluorescence emission anisotropy probe.

PubMed Central

Davenport, L; Targowski, P

1996-01-01

The use of the long-lived fluorescence probe coronene (mean value of tau(FL) approximately 200 ns) is described for investigating submicrosecond lipid dynamics in DPPC model bilayer systems occurring below the lipid phase transition. Time-resolved fluorescence emission anisotropy decay profiles, measures as a function of increasing temperature toward the lipid-phase transition temperature (T(C)), for coronene-labeled DPPC small unilamellar vesicles (SUVs), are best described in most cases by three rotational decay components (phi(i = 3)). We have interpreted these data using two dynamic lipid bilayer models. In the first, a compartmental model, the long correlation time (phi(N)) is assigned to immobilized coronene molecules located in "gel-like" or highly ordered lipid phases (S-->1) of the bilayer, whereas a second fast rotational time (phi(F) approximately 2-5 ns) is associated with probes residing in more "fluid-like" regions (with corresponding lower ordering, S-->0). Interests here have focused on the origins of an intermediate correlation time (50-100 ns), the associated amplitude (beta(G)) of which increases with increasing temperature. Such behavior suggests a changing rotational environment surrounding the coronene molecules, arising from fluidization of gel lipid. The observed effective correlation time (phi(EFF)) thus reflects a discrete gel-fluid lipid exchange rate (k(FG)). A refinement of the compartmental model invokes a distribution of gel-fluid exchange rates (d(S,T)) corresponding to a distribution of lipid order parameters and is based on an adapted Landau expression for describing "gated" packing fluctuations. A total of seven parameters (five thermodynamic quantities, defined by the free energy versus temperature expansion; one gating parameter (gamma) defining a cooperative "melting" requirement; one limiting diffusion rate (or frequency factor: d(infinity))) suffice to predict complete anisotropy decay curves measured for coronene at several temperatures below the phospholipid T(C). The thermodynamic quantities are associated with the particular lipid of interest (in this case DPPC) and have been determined previously from ultrasound studies, thus representing fixed constants. Hence resolved variables are r(O), temperature-dependent gate parameters (gamma), and limiting diffusion rates (d(infinity)). This alternative distribution model is attractive because it provides a general probe-independent expression for distributed lipid fluctuation-induced probe rotational rates occurring within bilayer membranes below the phospholipid phase transition on the submicrosecond time scale. PMID:8889160

Cross-correlations between RMB exchange rate and international commodity markets

NASA Astrophysics Data System (ADS)

Lu, Xinsheng; Li, Jianfeng; Zhou, Ying; Qian, Yubo

2017-11-01

This paper employs multifractal detrended analysis (MF-DFA) and multifractal detrended cross-correlation analysis (MF-DCCA) to study cross-correlation behaviors between China's RMB exchange rate market and four international commodity markets, using a comprehensive set of data covering the period from 22 July 2005 to 15 March 2016. Our empirical results from MF-DFA indicate that the RMB exchange rate is the most inefficient among the 4 selected markets. The results from quantitative analysis have testified the existence of cross-correlations and the result from MF-DCCA have further confirmed a strong multifractal behavior between RMB exchange rate and international commodity markets. We also demonstrate that the recent financial crisis has significant impact on the cross-correlated behavior. Through the rolling window analysis, we find that the RMB exchange rates and international commodity prices are anti-persistent cross-correlated. The main sources of multifractality in the cross-correlations are long-range correlations between RMB exchange rate and the aggregate commodity, energy and metals index.

An extended model of vesicle fusion at the plasma membrane to estimate protein lateral diffusion from TIRF microscopy images.

PubMed

Basset, Antoine; Bouthemy, Patrick; Boulanger, Jérôme; Waharte, François; Salamero, Jean; Kervrann, Charles

2017-07-24

Characterizing membrane dynamics is a key issue to understand cell exchanges with the extra-cellular medium. Total internal reflection fluorescence microscopy (TIRFM) is well suited to focus on the late steps of exocytosis at the plasma membrane. However, it is still a challenging task to quantify (lateral) diffusion and estimate local dynamics of proteins. A new model was introduced to represent the behavior of cargo transmembrane proteins during the vesicle fusion to the plasma membrane at the end of the exocytosis process. Two biophysical parameters, the diffusion coefficient and the release rate parameter, are automatically estimated from TIRFM image sequences, to account for both the lateral diffusion of molecules at the membrane and the continuous release of the proteins from the vesicle to the plasma membrane. Quantitative evaluation on 300 realistic computer-generated image sequences demonstrated the efficiency and accuracy of the method. The application of our method on 16 real TIRFM image sequences additionally revealed differences in the dynamic behavior of Transferrin Receptor (TfR) and Langerin proteins. An automated method has been designed to simultaneously estimate the diffusion coefficient and the release rate for each individual vesicle fusion event at the plasma membrane in TIRFM image sequences. It can be exploited for further deciphering cell membrane dynamics.

Guided Autobiography's Developmental Exchange: What's in It for Me?

ERIC Educational Resources Information Center

Thornton, James E.; Collins, John B.; Birren, James E.; Svensson, Cheryl

2011-01-01

The developmental exchange is a central feature of social development, interpersonal dynamics, situated learning, and personal transformation. It is the enabling process in Guided Autobiography (GAB) settings that promotes the achievement of personal goals and group accomplishments. Nevertheless, these exchanges are embedded in the GAB structures…

Students' Verbal Exchanges and Dynamics during Sport Education

ERIC Educational Resources Information Center

Brock, Sheri; Hastie, Peter

2017-01-01

In physical education (PE), children frequently participate in teams and the exchanges that transpire shape their perspectives and subsequently, influence learning. While Sport Education is one pedagogical model designed to enhance social exchanges through team membership, we previously identified the need for additional research to monitor these…

SMC condensation centers in Bacillus subtilis are dynamic structures.

PubMed

Kleine Borgmann, Luise A K; Hummel, Hanna; Ulbrich, Maximilian H; Graumann, Peter L

2013-05-01

SMC and MukB complexes consist of a central SMC dimer and two essential binding partners, ScpA and ScpB (MukE and MukF), and are crucial for correct chromosome compaction and segregation. The complexes form two bipolar assemblies on the chromosome, one in each cell half. Using fluorescence recovery after photobleaching (FRAP), we provide evidence that the SMC complex has high exchange rates. This depends to a considerable degree on de novo protein synthesis, revealing that the bacterial SMC complex has high on and off rates for binding to the chromosome. A mutation in SMC that affects ATPase activity and results in exaggerated DNA binding in vitro causes a strong segregation defect in vivo and affects the localization of the entire SMC complex, which localizes to many more sites in the cell than under normal conditions. These data indicate that ATP turnover is important for the function of Bacillus subtilis SMC. In contrast, the centromere protein Spo0J and DNA gyrase showed much less exchange between distinct binding sites on the chromosome than that seen with SMC. Binding of Spo0J to the origin regions was rather static and remained partially conserved until the next cell cycle. Our experiments reveal that the SMC complex has a high, condensin-like turnover rate and that an alteration of the ATPase cycle affects SMC function in vivo, while several nucleoid-associated proteins feature limited or slow exchange between different sites on the nucleoid, which may be the basis for epigenetic-like phenomena observed in bacteria.

Asymmetric Preorganization of Inverted Pair Residues in the Sodium-Calcium Exchanger

PubMed Central

Giladi, Moshe; Almagor, Lior; van Dijk, Liat; Hiller, Reuben; Man, Petr; Forest, Eric; Khananshvili, Daniel

2016-01-01

In analogy with many other proteins, Na+/Ca2+ exchangers (NCX) adapt an inverted twofold symmetry of repeated structural elements, while exhibiting a functional asymmetry by stabilizing an outward-facing conformation. Here, structure-based mutant analyses of the Methanococcus jannaschii Na+/Ca2+ exchanger (NCX_Mj) were performed in conjunction with HDX-MS (hydrogen/deuterium exchange mass spectrometry) to identify the structure-dynamic determinants of functional asymmetry. HDX-MS identified hallmark differences in backbone dynamics at ion-coordinating residues of apo-NCX_Mj, whereas Na+or Ca2+ binding to the respective sites induced relatively small, but specific, changes in backbone dynamics. Mutant analysis identified ion-coordinating residues affecting the catalytic capacity (kcat/Km), but not the stability of the outward-facing conformation. In contrast, distinct “noncatalytic” residues (adjacent to the ion-coordinating residues) control the stability of the outward-facing conformation, but not the catalytic capacity. The helix-breaking signature sequences (GTSLPE) on the α1 and α2 repeats (at the ion-binding core) differ in their folding/unfolding dynamics, while providing asymmetric contributions to transport activities. The present data strongly support the idea that asymmetric preorganization of the ligand-free ion-pocket predefines catalytic reorganization of ion-bound residues, where secondary interactions with adjacent residues couple the alternating access. These findings provide a structure-dynamic basis for ion-coupled alternating access in NCX and similar proteins. PMID:26876271

Faster protein folding using enhanced conformational sampling of molecular dynamics simulation.

PubMed

Kamberaj, Hiqmet

2018-05-01

In this study, we applied swarm particle-like molecular dynamics (SPMD) approach to enhance conformational sampling of replica exchange simulations. In particular, the approach showed significant improvement in sampling efficiency of conformational phase space when combined with replica exchange method (REM) in computer simulation of peptide/protein folding. First we introduce the augmented dynamical system of equations, and demonstrate the stability of the algorithm. Then, we illustrate the approach by using different fully atomistic and coarse-grained model systems, comparing them with the standard replica exchange method. In addition, we applied SPMD simulation to calculate the time correlation functions of the transitions in a two dimensional surface to demonstrate the enhancement of transition path sampling. Our results showed that folded structure can be obtained in a shorter simulation time using the new method when compared with non-augmented dynamical system. Typically, in less than 0.5 ns using replica exchange runs assuming that native folded structure is known and within simulation time scale of 40 ns in the case of blind structure prediction. Furthermore, the root mean square deviations from the reference structures were less than 2Å. To demonstrate the performance of new method, we also implemented three simulation protocols using CHARMM software. Comparisons are also performed with standard targeted molecular dynamics simulation method. Copyright © 2018 Elsevier Inc. All rights reserved.

47 CFR 54.902 - Calculation of Interstate Common Line Support for transferred exchanges.

Code of Federal Regulations, 2012 CFR

2012-10-01

... exchanges. (a) In the event that a rate-of-return carrier acquires exchanges from an entity that is also a... actual data filed pursuant to § 54.903(a)(4) shall reflect the transfer of exchanges. All post....903(b)(3). (b) In the event that a rate-of-return carrier acquires exchanges from a price cap carrier...

Molecular dynamic heterogeneity of confined lipid films by 1H magnetization-exchange nuclear magnetic resonance

NASA Astrophysics Data System (ADS)

Buda, A.; Demco, D. E.; Jagadeesh, B.; Blümich, B.

2005-01-01

The molecular dynamic heterogeneity of monolayer to submonolayer thin lecithin films confined to submicron cylindrical pores were investigated by 1H magnetization exchange nuclear magnetic resonance. In this experiment a z-magnetization gradient was generated by a double-quantum dipolar filter. The magnetization-exchange decay and buildup curves were interpreted with the help of a theoretical model based on the approximation of a one-dimensional spin-diffusion process in a three-domain morphology. The dynamic heterogeneity of the fatty acid chains and the effects of the surface area per molecule, the diameter of the pores, and the temperature were characterized with the help of local spin-diffusion coefficients. The effect of various parameters on the molecular dynamics of the mobile region of the fatty acid chains was quantified by introducing an ad hoc Gaussian distribution function of the 1H residual dipolar couplings. For the lipid films investigated in this study, the surface induced order and the geometrical confinement affect the chain dynamics of the entire molecule. Therefore, each part of the chain independently reflects the effect of surface coverage, pore size, and temperature.

Experimental studies of alunite: II. Rates of alunite-water alkali and isotope exchange

USGS Publications Warehouse

Stoffregen, R.E.; Rye, R.O.; Wasserman, M.D.

1994-01-01

Rates of alkali exchange between alunite and water have been measured in hydrothermal experiments of 1 hour to 259 days duration at 150 to 400??C. Examination of run products by scanning electron microscope indicates that the reaction takes place by dissolution-reprecipitation. This exchange is modeled with an empirical rate equation which assumes a linear decrease in mineral surface area with percent exchange (f) and a linear dependence of the rate on the square root of the affinity for the alkali exchange reaction. This equation provides a good fit of the experimental data for f = 17% to 90% and yields log rate constants which range from -6.25 moles alkali m-2s-1 at 400??C to - 11.7 moles alkali m-2s-1 at 200??C. The variation in these rates with temperature is given by the equation log k* = -8.17(1000/T(K)) + 5.54 (r2 = 0.987) which yields an activation energy of 37.4 ?? 1.5 kcal/mol. For comparison, data from O'Neil and Taylor (1967) and Merigoux (1968) modeled with a pseudo-second-order rate expression give an activation energy of 36.1 ?? 2.9 kcal/mol for alkali-feldspar water Na-K exchange. In the absence of coupled alkali exchange, oxygen isotope exchange between alunite and water also occurs by dissolution-reprecipitation but rates are one to three orders of magnitude lower than those for alkali exchange. In fine-grained alunites, significant D-H exchange occurs by hydrogen diffusion at temperatures as low as 100??C. Computed hydrogen diffusion coefficients range from -15.7 to -17.3 cm2s-1 and suggest that the activation energy for hydrogen diffusion may be as low as 6 kcal/mol. These experiments indicate that rates of alkali exchange in the relatively coarse-grained alunites typical of hydrothermal ore deposits are insignificant, and support the reliability of K-Ar age data from such samples. However, the fine-grained alunites typical of low temperature settings may be susceptible to limited alkali exchange at surficial conditions which could cause alteration of their radiometric ages. Furthermore, the rapid rate of hydrogen diffusion observed at 100-150??C suggests that fine-grained alunites are susceptible to rapid D-H re-equilibration even at surficial conditions. ?? 1994.

Institutional Communication Dynamics in Instructional Effectiveness: Development of a Student Self-Report Measure of FVP, LMX, and TMX in a Pedagogical Context

ERIC Educational Resources Information Center

Lucas, Aaron D.; Voss, Roger Alan; Krumwiede, Dennis W.

2015-01-01

Fractal vertical polarization (FVP) has joined leader-member exchange (LMX) and team member exchange (TMX) as one of the available models of communication dynamics based on complexity theory, which now all benefit from valid scales for use in organizational settings. The purpose of these models is to assess the quality of interpersonal information…

Contributions of chemical exchange to T1ρ dispersion in a tissue model.

PubMed

Cobb, Jared G; Xie, Jingping; Gore, John C

2011-12-01

Variations in T(1ρ) with locking-field strength (T(1ρ) dispersion) may be used to estimate proton exchange rates. We developed a novel approach utilizing the second derivative of the dispersion curve to measure exchange in a model system of cross-linked polyacrylamide gels. These gels were varied in relative composition of comonomers, increasing stiffness, and in pH, modifying exchange rates. Magnetic resonance images were recorded with a spin-locking sequence as described by Sepponen et al. These measurements were fit to a mono-exponential decay function yielding values for T(1ρ) at each locking-field measured. These values were then fit to a model by Chopra et al. for estimating exchange rates. For low stiffness gels, the calculated exchange values increased by a factor of 4 as pH increased, consistent with chemical exchange being the dominant contributor to T(1ρ) dispersion. Interestingly, calculated chemical exchange rates also increased with stiffness, likely due to modified side-chain exchange kinetics as the composition varied. This article demonstrates a new method to assess the structural and chemical effects on T(1ρ) relaxation dispersion with a suitable model. These phenomena may be exploited in an imaging context to emphasize the presence of nuclei of specific exchange rates, rather than chemical shifts. Copyright © 2011 Wiley Periodicals, Inc.

Nest odor dynamics in the social wasp Vespula vulgaris

NASA Astrophysics Data System (ADS)

Steinmetz, Inge; Schmolz, Erik

2005-09-01

We investigated nest odor dynamics in the common yellow jacket, Vespula vulgaris. In six isolated colonies, we tested the aggression rates toward dead nestmates that had been stored for 10 min, 10 and 19 days outside their colonies at 76 °C. The aggression rate increased from about 12% toward recently killed nestmates up to 30% toward nestmates killed 19 days before the experiment. Obviously, the conserved nest odor profile of the nestmates frozen for several days did not match with that of their colony anymore. This indicates a change of the nest odor within the colony. In a second experiment, we kept two colonies each in one nest box with a complete separation of both neighbor nests by a solid wall inside the box for 28 days. In confrontation experiments, the colony members treated dead foragers from the neighbor nest as aggressively as dead foreign, non-neighbor workers (about 39% each) whereas only about 14% reacted aggressively toward dead nestmates. Seventeen days after the replacement of the solid wall by a metallic grid, which allowed no physical contact but air exchange between the two neighbor colonies, the aggression rates toward foreign workers and nestmates remained relatively unaffected whereas it decreased significantly toward dead neighbors to about 11%. These results suggest a nest odor dynamic caused by volatiles transferred between two adjacent colonies, resulting in an equalization of the former colony specific nest odors. A change of nest odor dynamics influenced by volatiles was so far described only for one ant species at all.

Environmental variation, vegetation distribution, carbon dynamics and water/energy exchange at high latitudes

USGS Publications Warehouse

McGuire, A.D.; Wirth, C.; Apps, M.; Beringer, J.; Clein, J.; Epstein, H.; Kicklighter, D.W.; Bhatti, J.; Chapin, F. S.; De Groot, B.; Efremov, D.; Eugster, W.; Fukuda, M.; Gower, T.; Hinzman, L.; Huntley, B.; Jia, G.J.; Kasischke, E.; Melillo, J.; Romanovsky, V.; Shvidenko, A.; Vaganov, E.; Walker, D.

2002-01-01

The responses of high latitude ecosystems to global change involve complex interactions among environmental variables, vegetation distribution, carbon dynamics, and water and energy exchange. These responses may have important consequences for the earth system. In this study, we evaluated how vegetation distribution, carbon stocks and turnover, and water and energy exchange are related to environmental variation spanned by the network of the IGBP high latitude transects. While the most notable feature of the high latitude transects is that they generally span temperature gradients from southern to northern latitudes, there are substantial differences in temperature among the transects. Also, along each transect temperature co-varies with precipitation and photosynthetically active radiation, which are also variable among the transects. Both climate and disturbance interact to influence latitudinal patterns of vegetation and soil carbon storage among the transects, and vegetation distribution appears to interact with climate to determine exchanges of heat and moisture in high latitudes. Despite limitations imposed by the data we assembled, the analyses in this study have taken an important step toward clarifying the complexity of interactions among environmental variables, vegetation distribution, carbon stocks and turnover, and water and energy exchange in high latitude regions. This study reveals the need to conduct coordinated global change studies in high latitudes to further elucidate how interactions among climate, disturbance, and vegetation distribution influence carbon dynamics and water and energy exchange in high latitudes.

Exchange-mediated contrast in CEST and spin-lock imaging.

PubMed

Cobb, Jared Guthrie; Li, Ke; Xie, Jingping; Gochberg, Daniel F; Gore, John C

2014-01-01

Magnetic resonance images of biological media based on chemical exchange saturation transfer (CEST) show contrast that depends on chemical exchange between water and other protons. In addition, spin-lattice relaxation rates in the rotating frame (R1ρ) are also affected by exchange, especially at high fields, and can be exploited to provide novel, exchange-dependent contrast. Here, we evaluate and compare the factors that modulate the exchange contrast for these methods using simulations and experiments on simple, biologically relevant samples. Simulations and experimental measurements at 9.4 T of rotating frame relaxation rate dispersion and CEST contrast were performed on solutions of macromolecules containing amide and hydroxyl exchanging protons. The simulations and experimental measurements confirm that both CEST and R1ρ measurements depend on similar exchange parameters, but they manifest themselves differently in their effects on contrast. CEST contrast may be larger in the slow and intermediate exchange regimes for protons with large resonant frequency offsets (e.g. >2 ppm). Spin-locking techniques can produce larger contrast enhancement when resonant frequency offsets are small (<2 ppm) and exchange is in the intermediate-to-fast regime. The image contrasts scale differently with field strength, exchange rate and concentration. CEST and R1ρ measurements provide different and somewhat complementary information about exchange in tissues. Whereas CEST can depict exchange of protons with specific chemical shifts, appropriate R1ρ-dependent acquisitions can be employed to selectively portray protons of specific exchange rates. © 2013.

Exchange-Mediated Contrast in CEST and Spin-Lock Imaging

PubMed Central

Cobb, Jared Guthrie; Li, Ke; Xie, Jingping; Gochberg, Daniel F.; Gore, John C.

2014-01-01

PURPOSE Magnetic resonance images of biological media based on chemical exchange saturation transfer (CEST) show contrast that depends on chemical exchange between water and other protons. In addition, spin-lattice relaxation rates in the rotating frame (R1ρ) are also affected by exchange, especially at high fields, and can be exploited to provide novel, exchange-dependent contrast. Here, we evaluate and compare the factors that modulate the exchange contrast for these methods using simulations and experiments on simple, biologically relevant samples. METHODS Simulations and experimental measurements at 9.4T of rotating frame relaxation rate dispersion and CEST contrast were performed on solutions of macromolecules containing amide and hydroxyl exchanging protons. RESULTS The simulations and experimental measurements confirm that both CEST and R1ρ measurements depend on similar exchange parameters, but they manifest themselves differently in their effects on contrast. CEST contrast may be larger in the slow and intermediate exchange regimes for protons with large resonant frequency offsets (e.g. > 2ppm). Spin-locking techniques can produce larger contrast enhancement when resonant frequency offsets are small (< 2 ppm) and exchange is in the intermediate to fast regime. The image contrasts scale differently with field strength, exchange rate and concentration. CONCLUSION CEST and R1ρ measurements provide different and somewhat complementary information about exchange in tissues. Whereas CEST can depict exchange of protons with specific chemical shifts, appropriate R1ρ dependent acquisitions can be employed to selectively portray protons of specific exchange rates. PMID:24239335

Pilot study of oxygen transport rate of banked red blood cells.

PubMed

Buchwald, H; Menchaca, H J; Michalek, V N; Rudser, K D; Rohde, T D; O'Dea, T; Connett, J E; Gorlin, J

2009-01-01

Dynamic oximetry provides a new way to assess the effect of blood storage on the oxygen transport rate (OTR). In dynamic oximetry, the rate at which oxyhemoglobin becomes deoxyhemoglobin is measured optically, thereby, indirectly measuring the rate at which oxygen leaves the red blood cell (RBC) making it available for transfer to tissues. Extending the physiologic diffusion time in an in vitro apparatus, consisting of a diffusion system and gas exchanger capable of controlling the surface area and the time of exposure for oxygenation and deoxygenation, makes OTR measurement feasible. Eight normal blood donor units, collected in adenine, dextrose, sorbitol, sodium chloride and mannitol , were stored for 8 weeks under standard conditions and serially sampled for OTR. We report that the OTR at the time of blood bank donation appears to be singular for each donor, that the interdonor differences are maintained over time, and that the individual OTR increased 1.72-fold (95% CI 1.51, 1.95) over 8 weeks, adjusting for sex, age and plasma cholesterol level. Oxygen transport rate increases during storage; blood units with similar haemoglobin content may have significant differences in OTR. Studies examining blood parameters at the time of donation and blood storage on patient outcomes should consider measuring OTR, as it may contribute to differences in observed efficacy of tissue oxygenation.

Modeling whole-tree carbon assimilation rate using observed transpiration rates and needle sugar carbon isotope ratios.

PubMed

Hu, Jia; Moore, David J P; Riveros-Iregui, Diego A; Burns, Sean P; Monson, Russell K

2010-03-01

*Understanding controls over plant-atmosphere CO(2) exchange is important for quantifying carbon budgets across a range of spatial and temporal scales. In this study, we used a simple approach to estimate whole-tree CO(2) assimilation rate (A(Tree)) in a subalpine forest ecosystem. *We analysed the carbon isotope ratio (delta(13)C) of extracted needle sugars and combined it with the daytime leaf-to-air vapor pressure deficit to estimate tree water-use efficiency (WUE). The estimated WUE was then combined with observations of tree transpiration rate (E) using sap flow techniques to estimate A(Tree). Estimates of A(Tree) for the three dominant tree species in the forest were combined with species distribution and tree size to estimate and gross primary productivity (GPP) using an ecosystem process model. *A sensitivity analysis showed that estimates of A(Tree) were more sensitive to dynamics in E than delta(13)C. At the ecosystem scale, the abundance of lodgepole pine trees influenced seasonal dynamics in GPP considerably more than Engelmann spruce and subalpine fir because of its greater sensitivity of E to seasonal climate variation. *The results provide the framework for a nondestructive method for estimating whole-tree carbon assimilation rate and ecosystem GPP over daily-to weekly time scales.

Large-Scale Conformational Dynamics Control H5N1 Influenza Polymerase PB2 Binding to Importin α.

PubMed

Delaforge, Elise; Milles, Sigrid; Bouvignies, Guillaume; Bouvier, Denis; Boivin, Stephane; Salvi, Nicola; Maurin, Damien; Martel, Anne; Round, Adam; Lemke, Edward A; Jensen, Malene Ringkjøbing; Hart, Darren J; Blackledge, Martin

2015-12-09

Influenza A RNA polymerase complex is formed from three components, PA, PB1, and PB2. PB2 is independently imported into the nucleus prior to polymerase reconstitution. All crystallographic structures of the PB2 C-terminus (residues 536-759) reveal two globular domains, 627 and NLS, that form a tightly packed heterodimer. The molecular basis of the affinity of 627-NLS for importins remained unclear from these structures, apparently requiring large-scale conformational changes prior to importin binding. Using a combination of solution-state NMR, small-angle neutron scattering, small-angle X-ray scattering (SAXS), and Förster resonance energy transfer (FRET), we show that 627-NLS populates a temperature-dependent dynamic equilibrium between closed and open states. The closed state is stabilized by a tripartite salt bridge involving the 627-NLS interface and the linker, that becomes flexible in the open state, with 627 and NLS dislocating into a highly dynamic ensemble. Activation enthalpies and entropies associated with the rupture of this interface were derived from simultaneous analysis of temperature-dependent chemical exchange saturation transfer measurements, revealing a strong temperature dependence of both open-state population and exchange rate. Single-molecule FRET and SAXS demonstrate that only the open-form is capable of binding to importin α and that, upon binding, the 627 domain samples a dynamic conformational equilibrium in the vicinity of the C-terminus of importin α. This intrinsic large-scale conformational flexibility therefore enables 627-NLS to bind importin through conformational selection from a temperature-dependent equilibrium comprising both functional forms of the protein.

Design and simulation of heat exchangers using Aspen HYSYS, and Aspen exchanger design and rating for paddy drying application

NASA Astrophysics Data System (ADS)

Janaun, J.; Kamin, N. H.; Wong, K. H.; Tham, H. J.; Kong, V. V.; Farajpourlar, M.

2016-06-01

Air heating unit is one of the most important parts in paddy drying to ensure the efficiency of a drying process. In addition, an optimized air heating unit does not only promise a good paddy quality, but also save more for the operating cost. This study determined the suitable and best specifications heating unit to heat air for paddy drying in the LAMB dryer. In this study, Aspen HYSYS v7.3 was used to obtain the minimum flow rate of hot water needed. The resulting data obtained from Aspen HYSYS v7.3 were used in Aspen Exchanger Design and Rating (EDR) to generate heat exchanger design and costs. The designs include shell and tubes and plate heat exchanger. The heat exchanger was designed in order to produce various drying temperatures of 40, 50, 60 and 70°C of air with different flow rate, 300, 2500 and 5000 LPM. The optimum condition for the heat exchanger were found to be plate heat exchanger with 0.6 mm plate thickness, 198.75 mm plate width, 554.8 mm plate length and 11 numbers of plates operating at 5000 LPM air flow rate.

Protein Allostery and Conformational Dynamics.

PubMed

Guo, Jingjing; Zhou, Huan-Xiang

2016-06-08

The functions of many proteins are regulated through allostery, whereby effector binding at a distal site changes the functional activity (e.g., substrate binding affinity or catalytic efficiency) at the active site. Most allosteric studies have focused on thermodynamic properties, in particular, substrate binding affinity. Changes in substrate binding affinity by allosteric effectors have generally been thought to be mediated by conformational transitions of the proteins or, alternatively, by changes in the broadness of the free energy basin of the protein conformational state without shifting the basin minimum position. When effector binding changes the free energy landscape of a protein in conformational space, the change affects not only thermodynamic properties but also dynamic properties, including the amplitudes of motions on different time scales and rates of conformational transitions. Here we assess the roles of conformational dynamics in allosteric regulation. Two cases are highlighted where NMR spectroscopy and molecular dynamics simulation have been used as complementary approaches to identify residues possibly involved in allosteric communication. Perspectives on contentious issues, for example, the relationship between picosecond-nanosecond local and microsecond-millisecond conformational exchange dynamics, are presented.

Rethinking exchange market models as optimization algorithms

NASA Astrophysics Data System (ADS)

Luquini, Evandro; Omar, Nizam

2018-02-01

The exchange market model has mainly been used to study the inequality problem. Although the human society inequality problem is very important, the exchange market models dynamics until stationary state and its capability of ranking individuals is interesting in itself. This study considers the hypothesis that the exchange market model could be understood as an optimization procedure. We present herein the implications for algorithmic optimization and also the possibility of a new family of exchange market models

Biosphere/atmosphere CO2 exchange in tundra ecosystems - Community characteristics and relationships with multispectral surface reflectance

NASA Technical Reports Server (NTRS)

Whiting, Gary J.; Bartlett, David S.; Fan, Song-Miao; Bakwin, Peter S.; Wofsy, Steven C.

1992-01-01

CO2 exchange rates were measured at selected tundra sites near Bethel, Alaska using portable, climate-controlled, instrumented enclosures. The empirically modeled exchange rate for a representative area of vegetated tundra was 1.2 +/- 1.2 g/sq m/d, compared to a tower-measured exchange over the same time period of 1.1 +.0- 1.2 g/sq m/d. Net exchange in response to varying light levels was compared to wet meadow and dry upland tundra, and to the net exchange measured by the micrometeoroidal tower technique. The multispectral reflectance properties of the sites were measured and related to exchange rates in order to provide a quantitative foundation for the use of satellite remote sensing to monitor biosphere/atmosphere CO2 exchange in the tundra biome.

Is the surface oxygen exchange rate linked to bulk ion diffusivity in mixed conducting Ruddlesden–Popper phases?

DOE PAGES

Tomkiewicz, Alex C.; Tamimi, Mazin A.; Huq, Ashfia; ...

2015-03-02

There is a possible link between oxygen surface exchange rate and bulk oxygen anion diffusivity in mixed ionic and electronic conducting oxides; it is a topic of great interest and debate. While a large body of experimental evidence and theoretical analyses support a link, observed differences between bulk and surface composition of these materials are hard to reconcile with this observation. This is further compounded by potential problems with simultaneous measurement of both parameters. Here we utilize separate techniques, in situ neutron diffraction and pulsed isotopic surface exchange, to examine bulk ion mobility and surface oxygen exchange rates of threemore » Ruddlesden-Popper phases, general form A n-1A 2'BnO 3n+1, A n-1A 2'BnX 3n+1; LaSrCo 0.5Fe 0.5O 4-δ (n = 1), La 0.3Sr 2.7CoFeO 7-δ (n = 2) and LaSr 3Co 1.5Fe 1.5O 10-δ (n = 3). These measurements are complemented by surface composition determination via high sensitivity-low energy ion scattering. We observe a correlation between bulk ion mobility and surface exchange rate between materials. The surface exchange rates vary by more than one order of magnitude with high anion mobility in the bulk of an oxygen vacancy-rich n = 2 Ruddlesden-Popper material correlating with rapid oxygen exchange. Furthermore this is in contrast with the similar surface exchange rates which we may expect due to similar surface compositions across all three samples. This paper conclude that experimental limitations lead to inherent convolution of surface and bulk rates, and that surface exchange steps are not likely to be rate limiting in oxygen incorporation.« less

Short-duration respirometry underestimates metabolic rate for discontinuous breathers.

PubMed

Winwood-Smith, Hugh S; White, Craig R

2018-06-07

Metabolic rate is commonly estimated from rates of gas exchange. An underappreciated factor that can influence estimates is patterns of pulmonary respiration. Amphibians display discontinuous respiratory patterns, often including long apnoeas, in addition to cutaneous gas exchange. The contribution of cutaneous exchange increases at low temperatures when metabolic rate is low. Due to the relatively low permeability of skin, measurements that disproportionately capture cutaneous exchange can produce underestimates of metabolic rate. The permeability of amphibian skin to CO 2 is greater than O 2 , therefore calculating the ratio of whole-animal CO 2 emission to O 2 uptake (the respiratory exchange ratio, RER) can be used to avoid underestimates of metabolic rate by ensuring that observed values of RER fall within the normal physiological range (∼0.7 to 1). Using data for cane toads Rhinella marina we show that short-duration measurements lead to underestimates of metabolic rate and overestimates of RER. At low temperatures this problem is exacerbated, requiring over 12 hours for RER to fall within the normal physiological range. Many published values of metabolic rate in animals that utilise cutaneous exchange may be underestimates. © 2018. Published by The Company of Biologists Ltd.

Review of Air Exchange Rate Models for Air Pollution Exposure Assessments

EPA Science Inventory

A critical aspect of air pollution exposure assessments is estimation of the air exchange rate (AER) for various buildings, where people spend their time. The AER, which is rate the exchange of indoor air with outdoor air, is an important determinant for entry of outdoor air pol...

Dynamics of leaf gas exchange, xylem and phloem transport, water potential and carbohydrate concentration in a realistic 3-D model tree crown.

PubMed

Nikinmaa, Eero; Sievänen, Risto; Hölttä, Teemu

2014-09-01

Tree models simulate productivity using general gas exchange responses and structural relationships, but they rarely check whether leaf gas exchange and resulting water and assimilate transport and driving pressure gradients remain within acceptable physical boundaries. This study presents an implementation of the cohesion-tension theory of xylem transport and the Münch hypothesis of phloem transport in a realistic 3-D tree structure and assesses the gas exchange and transport dynamics. A mechanistic model of xylem and phloem transport was used, together with a tested leaf assimilation and transpiration model in a realistic tree architecture to simulate leaf gas exchange and water and carbohydrate transport within an 8-year-old Scots pine tree. The model solved the dynamics of the amounts of water and sucrose solute in the xylem, cambium and phloem using a fine-grained mesh with a system of coupled ordinary differential equations. The simulations predicted the observed patterns of pressure gradients and sugar concentration. Diurnal variation of environmental conditions influenced tree-level gradients in turgor pressure and sugar concentration, which are important drivers of carbon allocation. The results and between-shoot variation were sensitive to structural and functional parameters such as tree-level scaling of conduit size and phloem unloading. Linking whole-tree-level water and assimilate transport, gas exchange and sink activity opens a new avenue for plant studies, as features that are difficult to measure can be studied dynamically with the model. Tree-level responses to local and external conditions can be tested, thus making the approach described here a good test-bench for studies of whole-tree physiology.

Ventilation Control of Volatile Organic Compounds in New U.S. Homes: Results of a Controlled Field Study in Nine Residential Units

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

Willem, Henry; Hult, Erin L.; Hotchi, Toshifumi

2013-01-01

In order to optimize strategies to remove airborne contaminants in residences, it is necessary to determine how contaminant concentrations respond to changes in the air exchange rate. The impact of air exchange rate on the indoor concentrations of 39 target volatile organic compounds (VOCs) was assessed by measuring air exchange rates and VOC concentrations at three ventilation settings in nine residences. Active sampling methods were used for VOC concentration measurements, and passive perfluorocarbon tracer gas emitters with active sampling were used to determine the overall air exchange rate corresponding to the VOC measurements at each ventilation setting. The concentration levelsmore » and emission rates of the target VOCs varied by as much as two orders of magnitude across sites. Aldehyde and terpene compounds were typically the chemical classes with highest concentrations, followed by alkanes, aromatics, and siloxanes. For each home, VOC concentrations tended to decrease as the air exchange rate was increased, however, measurement uncertainty was significant. The indoor concentration was inversely proportional to air exchange rate for most compounds. For a subset of compounds including formaldehyde, however, the indoor concentration exhibited a non-linear dependence on the timescale for air exchange« less

Ventilation Control of Volatile Organic Compounds in New U.S. Homes: Results of a Controlled Field Study in Nine Residential Units

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

Willem, Henry; Hult, Erin L.; Hotchi, Toshifumi

2013-01-23

In order to optimize strategies to remove airborne contaminants in residences, it is necessary to determine how contaminant concentrations respond to changes in the air exchange rate. The impact of air exchange rate on the indoor concentrations of 39 target volatile organic compounds (VOCs) was assessed by measuring air exchange rates and VOC concentrations at three ventilation settings in nine residences. Active sampling methods were used for VOC concentration measurements, and passive perfluorocarbon tracer gas emitters with active sampling were used to determine the overall air exchange rate corresponding to the VOC measurements at each ventilation setting. The concentration levelsmore » and emission rates of the target VOCs varied by as much as two orders of magnitude across sites. Aldehyde and terpene compounds were typically the chemical classes with highest concentrations, followed by alkanes, aromatics, and siloxanes. For each home, VOC concentrations tended to decrease as the air exchange rate was increased, however, measurement uncertainty was significant. The indoor concentration was inversely proportional to air exchange rate for most compounds. For a subset of compounds including formaldehyde, however, the indoor concentration exhibited a non-linear dependence on the timescale for air exchange.« less

Dynamic studies of H-Ras•GTPγS interactions with nucleotide exchange factor Sos reveal a transient ternary complex formation in solution

PubMed Central

Vo, Uybach; Vajpai, Navratna; Embrey, Kevin J.; Golovanov, Alexander P.

2016-01-01

The cycling between GDP- and GTP- bound forms of the Ras protein is partly regulated by the binding of Sos. The structural/dynamic behavior of the complex formed between activated Sos and Ras at the point of the functional cycle where the nucleotide exchange is completed has not been described to date. Here we show that solution NMR spectra of H-Ras∙GTPγS mixed with a functional fragment of Sos (SosCat) at a 2:1 ratio are consistent with the formation of a rather dynamic assembly. H-Ras∙GTPγS binding was in fast exchange on the NMR timescale and retained a significant degree of molecular tumbling independent of SosCat, while SosCat also tumbled largely independently of H-Ras. Estimates of apparent molecular weight from both NMR data and SEC-MALS revealed that, at most, only one H-Ras∙GTPγS molecule appears stably bound to Sos. The weak transient interaction between Sos and the second H-Ras∙GTPγS may provide a necessary mechanism for complex dissociation upon the completion of the native GDP → GTP exchange reaction, but also explains measurable GTP → GTP exchange activity of Sos routinely observed in in vitro assays that use fluorescently-labelled analogs of GTP. Overall, the data presents the first dynamic snapshot of Ras functional cycle as controlled by Sos. PMID:27412770

A Dynamic Nutrient Budget of Subsystem Interactions in a Salt Marsh Estuary

NASA Astrophysics Data System (ADS)

Childers, Daniel L.; McKellar, Henry N.; Dame, Richard F.; Sklar, Fred H.; Blood, Elizabeth R.

1993-02-01

In tidal salt marsh estuaries, the different habitats of the ecosystem interact primarily through the tidal creek water column. These interactions include nutrient and materials exchanges with the salt marsh, oyster reefs, creek bottoms, and adjacent uplands. Nutrient budgets are often used to synthesize these kinds of subsystem exchange data, and are usually based on annual totals without accounting for nutrient variability at finer temporal resolutions. In this paper, we present a dynamic budget of carbon (C), nitrogen (N), and phosphorus (P) for the North Inlet estuary, South Carolina that synthesizes subsystem flux data in a new way. We have developed a dynamic budget that uses a tidal hydrology model to generate daily areas of inundated intertidal habitat (i.e. vegetated marsh and oyster reef) from tidal heights calculated hourly and combines them with flux data to determine a net daily input to, or removal from, the water column. Daily surpluses or deficits of each nutrient were compared with daily rates of change in observed tidally-averaged nutrient concentrations. Particular emphasis was placed on evaluating budget output from the intertidal subsystems. We compared our total annual budgets to values from syntheses of two North Inlet flux studies. Although areas of marsh inundated were 150-200 times greater than areas of oyster reef inundated, interactions per unit volume of estuarine water column were comparable in magnitude for soluble reactive P (SRP), particulate organic C (POC), and dissolved organic C (DOC). The marsh dominated the ammonium (NH +4) and nitrate + nitrite (NN) exchanges in the summer but the NH +4 and POC output were particularly sensitive to changes in oyster reef area. Winter and spring DOC release by the marsh coincided closely (in timing and magnitude) with the peak in DOC concentrations observed in the North Inlet estuary, suggesting that forest stream inputs of DOC are not nearly as important as has been hypothesized. Comparison of our budget predictions to a previous synthesis of the same subsytem flux data confirmed the power of using tidal hydrology to estimate subsystem interactions between sampling times. These comparisons also emphasized the importance of (1) water column processes to NH +4 dynamics (2) subtidal benthic fluxes to DOC dynamics, and (3) external inputs to NN dynamics. By incorporating our best current knowledge of estuary-wide subsystem areas, the dynamic budget also allowed us to link subsystem flux data to the results of a study quantifying exchanges between the estuary and the coastal ocean. That comparison indicated the shortcomings of any site-specific extrapolation to whole-system conclusions where a homogeneous ecosystem must be assumed. We used the differences between our total annual C, N, and P budgets and reported exports of those constituents from the system to generate hypotheses and suggest future research efforts both at North Inlet and southeastern salt marsh estuaries in general.

Ergodicity and model quality in template-restrained canonical and temperature/Hamiltonian replica exchange coarse-grained molecular dynamics simulations of proteins.

PubMed

Karczyńska, Agnieszka S; Czaplewski, Cezary; Krupa, Paweł; Mozolewska, Magdalena A; Joo, Keehyoung; Lee, Jooyoung; Liwo, Adam

2017-12-05

Molecular simulations restrained to single or multiple templates are commonly used in protein-structure modeling. However, the restraints introduce additional barriers, thus impairing the ergodicity of simulations, which can affect the quality of the resulting models. In this work, the effect of restraint types and simulation schemes on ergodicity and model quality was investigated by performing template-restrained canonical molecular dynamics (MD), multiplexed replica-exchange molecular dynamics, and Hamiltonian replica exchange molecular dynamics (HREMD) simulations with the coarse-grained UNRES force field on nine selected proteins, with pseudo-harmonic log-Gaussian (unbounded) or Lorentzian (bounded) restraint functions. The best ergodicity was exhibited by HREMD. It has been found that non-ergodicity does not affect model quality if good templates are used to generate restraints. However, when poor-quality restraints not covering the entire protein are used, the improved ergodicity of HREMD can lead to significantly improved protein models. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Field measurements on the exchange of carbonyl sulfide between lichens and the atmosphere

NASA Astrophysics Data System (ADS)

Kuhn, U.; Wolf, A.; Gries, C.; , T. H. Nash, III; Kesselmeier, J.

The exchange of carbonyl sulfide (COS) between lichens and the atmosphere was investigated under natural field conditions. Using dynamic enclosures flushed with ambient air, we demonstrate that lichens act as a major sink for atmospheric COS in the investigated ecosystem. Diel courses of the exchange are shown in an open oak woodland ecosystem at a rural site in central California. The measurements were distributed over a variety of weather conditions during the dry (May/June) and the wet season (Nov/Dec). The physiological parameters (CO 2 exchange and thallus hydration status) plus environmental variables (temperature, irradiance, atmospheric humidity and ambient COS mixing ratio) were recorded. Lichens are capable of continuous uptake of COS in the dark as well as in the light, depending mainly on their moisture status. Results indicate that the uptake is additionally dependent on temperature and COS ambient mixing ratio. Enzyme inactivation by high temperature denaturation demonstrate that the uptake is under physiological control. Light and thus photosynthetic activity do not have a direct influence on the uptake rate. Under these field investigations the COS uptake on a dry weight basis ranged between 0.015 and 0.071 pmol g-1 s-1. On a thallus surface area basis the sink strength is comparable to the uptake by higher vegetation.

Experimental study on heat transfer performance of fin-tube exchanger and PSHE for waste heat recovery

NASA Astrophysics Data System (ADS)

Chen, Ting; Bae, Kyung Jin; Kwon, Oh Kyung

2018-02-01

In this paper, heat transfer characteristics of fin-tube heat exchanger and primary surface heat exchanger (PSHE) used in waste heat recovery were investigated experimentally. The flow in the fin-tube heat exchanger is cross flow and in PSHE counter flow. The variations of friction factor and Colburn j factor with air mass flow rate, and Nu number with Re number are presented. Various comparison methods are used to evaluate heat transfer performance, and the results show that the heat transfer rate of the PSHE is on average 17.3% larger than that of fin-tube heat exchanger when air mass flow rate is ranging from 1.24 to 3.45 kg/min. However, the PSHE causes higher pressure drop, and the fin-tube heat exchanger has a wider application range which leads to a 31.7% higher value of maximum heat transfer rate compared to that of the PSHE. Besides, under the same fan power per unit frontal surface, a higher heat transfer rate value is given in the fin-tube heat exchanger.

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

Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris

Controlling the heterolytic cleavage of the H-H bond of dihydrogen is critically important in catalytic hydrogenations and in the catalytic oxidation of H2. We show how the rate of reversible heterolytic cleavage of H2 can be controlled over nearly four orders of magnitude at 25 °C, from 2.1 × 103 s-1 to ≥107 s-1. Bifunctional Mo complexes, [CpMo(CO)(κ3-P2N2)]+ (P2N2 = 1,5-diaza-3,7-diphosphacyclooctane with alkyl/aryl groups on N and P), have been developed for heterolytic cleavage of H2 into a proton and a hydride, akin to Frustrated Lewis Pairs. The H-H bond cleavage is enabled by the basic amine in the secondmore » coordination sphere. The products of heterolytic cleavage of H2, Mo hydride complexes bearing protonated amines, [CpMo(H)(CO)(P2N2H)]+, were characterized by spectroscopic studies and by X-ray crystallography. Variable temperature 1H, 15N and 2-D 1H-1H ROESY NMR spectra indicated rapid exchange of the proton and hydride. The exchange rates are in the order [CpMo(H)(CO)(PPh2NPh2H)]+ > [CpMo(H)(CO)(PtBu2NPh2H)]+ > [CpMo(H)(CO)(PPh2NBn2H)]+ > [CpMo(H)(CO)(PtBu2NBn2H)]+ > [CpMo(H)(CO)(PtBu2NtBu2H)]+. The pKa values determined in acetonitrile range from 9.3 to 17.7, and show a linear correlation with the logarithm of the exchange rates. Thus the exchange dynamics are controlled through the relative acidity of the [CpMo(H)(CO)(P2N2H)]+ and [CpMo(H2)(CO)(P2N2)]+ isomers, providing a design principle for controlling heterolytic cleavage of H2.« less

Automatable Measurement of Gas Exchange Rate in Streams: Oxygen-Carbon Method

NASA Astrophysics Data System (ADS)

Pennington, R.; Haggerty, R.; Argerich, A.; Wondzell, S. M.

2015-12-01

Gas exchange rates between streams and the atmosphere are critically important to measurement of in-stream ecologic processes, as well as fate and transport of hazardous pollutants such as mercury and PCBs. Methods to estimate gas exchange rates include empirical relations to hydraulics, and direct injection of a tracer gas such as propane or SF6. Empirical relations are inconsistent and inaccurate, particularly for lower order, high-roughness streams. Gas injections are labor-intensive, and measured gas exchange rates are difficult to extrapolate in time since they change with discharge and stream geometry. We propose a novel method for calculation of gas exchange rates utilizing O2, pCO2, pH, and temperature data. Measurements, which can be automated using data loggers and probes, are made on the upstream and downstream end of the study reach. Gas exchange rates are then calculated from a solution to the transport equations for oxygen and dissolved inorganic carbon. Field tests in steep, low order, high roughness streams of the HJ Andrews Experimental Forest indicate the method to be viable along stream reaches with high downstream gas concentration gradients and high rates of gas transfer velocity. Automated and continuous collection of oxygen and carbonate chemistry data is increasingly common, thus the method may be used to estimate gas exchange rates through time, and is well suited for interactivity with databases.

Pulse EPR detection of lipid exchange between protein-rich raft and bulk domains in the membrane: methodology development and its application to studies of influenza viral membrane.

PubMed Central

Kawasaki, K; Yin, J J; Subczynski, W K; Hyde, J S; Kusumi, A

2001-01-01

A pulse saturation-recovery electron paramagnetic resonance (EPR) method has been developed that allows estimation of the exchange rates of a spin-labeled lipid between the bulk domain and the protein-rich membrane domain, in which the rate of collision between the spin label and molecular oxygen is reduced (slow-oxygen transport domain, or SLOT domain). It is based on the measurements of saturation-recovery signals of a lipid spin label as a function of concentrations of both molecular oxygen and the spin label. Influenza viral membrane, one of the simplest paradigms for the study of biomembranes, showed the presence of two membrane domains with slow and fast collision rates with oxygen (a 16-fold difference) at 30 degrees C. The outbound rate from and the inbound rate into the SLOT domain (or possibly the rate of the domain disintegration and formation) were estimated to be 7.7 x 10(4) and 4.6 x 10(4) s(-1), (15 micros residency time), respectively, indicating that the SLOT domain is highly dynamic and that the entire SLOT domain represents about one-third of the membrane area. Because the oxygen transport rate in the SLOT domain is a factor of two smaller than that in purple membrane, where bacteriorhodopsin is aggregated, we propose that the SLOT domain in the viral membrane is the cholesterol-rich raft domain stabilized by the trimers of hemagglutinin and/or the tetramers of neuraminidase. PMID:11159441

Flow-Induced New Channels of Energy Exchange in Multi-Scale Plasma Dynamics – Revisiting Perturbative Hybrid Kinetic-MHD Theory

PubMed Central

Shiraishi, Junya; Miyato, Naoaki; Matsunaga, Go

2016-01-01

It is found that new channels of energy exchange between macro- and microscopic dynamics exist in plasmas. They are induced by macroscopic plasma flow. This finding is based on the kinetic-magnetohydrodynamic (MHD) theory, which analyses interaction between macroscopic (MHD-scale) motion and microscopic (particle-scale) dynamics. The kinetic-MHD theory is extended to include effects of macroscopic plasma flow self-consistently. The extension is realised by generalising an energy exchange term due to wave-particle resonance, denoted by δ WK. The first extension is generalisation of the particle’s Lagrangian, and the second one stems from modification to the particle distribution function due to flow. These extensions lead to a generalised expression of δ WK, which affects the MHD stability of plasmas. PMID:27160346

QUESP and QUEST revisited - fast and accurate quantitative CEST experiments.

PubMed

Zaiss, Moritz; Angelovski, Goran; Demetriou, Eleni; McMahon, Michael T; Golay, Xavier; Scheffler, Klaus

2018-03-01

Chemical exchange saturation transfer (CEST) NMR or MRI experiments allow detection of low concentrated molecules with enhanced sensitivity via their proton exchange with the abundant water pool. Be it endogenous metabolites or exogenous contrast agents, an exact quantification of the actual exchange rate is required to design optimal pulse sequences and/or specific sensitive agents. Refined analytical expressions allow deeper insight and improvement of accuracy for common quantification techniques. The accuracy of standard quantification methodologies, such as quantification of exchange rate using varying saturation power or varying saturation time, is improved especially for the case of nonequilibrium initial conditions and weak labeling conditions, meaning the saturation amplitude is smaller than the exchange rate (γB 1  < k). The improved analytical 'quantification of exchange rate using varying saturation power/time' (QUESP/QUEST) equations allow for more accurate exchange rate determination, and provide clear insights on the general principles to execute the experiments and to perform numerical evaluation. The proposed methodology was evaluated on the large-shift regime of paramagnetic chemical-exchange-saturation-transfer agents using simulated data and data of the paramagnetic Eu(III) complex of DOTA-tetraglycineamide. The refined formulas yield improved exchange rate estimation. General convergence intervals of the methods that would apply for smaller shift agents are also discussed. Magn Reson Med 79:1708-1721, 2018. © 2017 International Society for Magnetic Resonance in Medicine. © 2017 International Society for Magnetic Resonance in Medicine.

Metabolic analyzer. [for Skylab mission

NASA Technical Reports Server (NTRS)

Perry, C. L.

1973-01-01

An apparatus is described for the measurement of metabolic rate and breathing dynamics in which inhaled and exhaled breath are sensed by sealed, piston-displacement type spirometers. These spirometers electrically measure the volume of inhaled and exhaled breath. A mass spectrometer analyzes simultaneously for oxygen, carbon dioxide, nitrogen, and water vapor. Circuits responsive to the outputs of the spirometers, mass spectrometer, temperature, pressure, and timing signals compute oxygen consumption, carbon dioxide production, minute volume, and respiratory exchange ratio. A selective indicator provides for readout of these data at predetermined cyclic intervals.

AR(p) -based detrended fluctuation analysis

NASA Astrophysics Data System (ADS)

Alvarez-Ramirez, J.; Rodriguez, E.

2018-07-01

Autoregressive models are commonly used for modeling time-series from nature, economics and finance. This work explored simple autoregressive AR(p) models to remove long-term trends in detrended fluctuation analysis (DFA). Crude oil prices and bitcoin exchange rate were considered, with the former corresponding to a mature market and the latter to an emergent market. Results showed that AR(p) -based DFA performs similar to traditional DFA. However, the former DFA provides information on stability of long-term trends, which is valuable for understanding and quantifying the dynamics of complex time series from financial systems.

Toward a new modeling of international economics: An attempt to reformulate an international trade model based on real option theory

NASA Astrophysics Data System (ADS)

Fujita, Yasunori

2007-09-01

Reformulation of economics by physics has been carried out intensively to reveal many features of the asset market, which were missed in the classical economic theories. The present paper attempts to shed new light on this field. That is, this paper aims at reformulating the international trade model by making use of the real option theory. Based on such a stochastic dynamic model, we examine how the fluctuation of the foreign exchange rate makes effect on the welfare of the exporting country.

Li + solvation and kinetics of Li +–BF 4 -/PF 6 - ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories

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

Chang, Tsun-Mei; Dang, Liem X.

Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ethylene carbonate (EC) exchange process between the first and second solvation shells around Li+ and the dissociation kinetics of ion pairs Li+-[BF4] and Li+-[PF6] in this solvent. We calculate the exchange rates using transition state theory and correct them with transmission coefficients computed by the reactive flux; Impey, Madden, and McDonald approaches; and Grote-Hynes theory. We found the residence times of EC around Li+ ions varied from 70 to 450 ps, depending on the correction method used. We found the relaxation times changed significantlymore » from Li+-[BF4] to Li+-[PF6] ion pairs in EC. Our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influence the dissociation kinetics of ion pairing. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.« less