Dissolution of quartz in aqueous basic solution, 106-236 C - Surface kinetics of 'perfect' crystallographic faces

NASA Technical Reports Server (NTRS)

Gratz, Andrew J.; Bird, Peter; Quiro, Glenn B.

1990-01-01

A highly accurate method, called the negative crystal method, for determining the rate of dissolution on specific crystallographic faces of crystals was developed, in which the dissolution rates of nominally perfect crystal faces are obtained by measuring the size of individual negative crystals during a sequence of dissolution steps. The method was applied to determine the apparent activation energy and rate constants for the dissolution of quartz in 0.01 M KOH solutions at temperatures from 106 to 236 C. Also investigated were the effects of hydroxyl activity and ionic strength. The apparent activation energies for the dissolution of the prism and of the rhomb were determined.

Reaction Kinetics of Phenolic Antioxidants toward Photoinduced Pyranine Free Radicals in Biological Models.

PubMed

Aspée, Alexis; Aliaga, Christian; Maretti, Luca; Zúñiga-Núñez, Daniel; Godoy, Jessica; Pino, Eduardo; Cárdenas-Jirón, Gloria; Lopez-Alarcon, Camilo; Scaiano, Juan C; Alarcon, Emilio I

2017-07-06

8-Hydroxy-1,3,6-pyrenetrisulfonic acid (pyranine, PyOH) free radicals were induced by laser excitation at visible wavelengths (470 nm). The photochemical process involves photoelectron ejection from PyO- to produce PyO• and PyO•- with maxima absorption at 450 and 510 nm, respectively. The kinetic rate constants for phenolic antioxidants with PyO•, determined by nanosecond time-resolved spectroscopy, were largely reliant on the ionic strength depending on the antioxidant phenol/phenolate dissociation constant. Further, the apparent rate constant measured in the presence of Triton X100 micelles was influenced by the antioxidant partition between the micelle and the dispersant aqueous media but limited by its exit rates from the micelle. Similarly, the rate reaction between ascorbic acid and PyO• was markedly affected by the presence of human serum albumin responding to the dynamic of the ascorbic acid binding to the protein.

Mechanism of block by tedisamil of transient outward current in human ventricular subepicardial myocytes

PubMed Central

Wettwer, Erich; Himmel, Herbert M; Amos, Gregory J; Li, Qi; Metzger, Franz; Ravens, Ursula

1998-01-01

Tedisamil is a new antiarrhythmic drug with predominant class III action. The aim of the present study was to investigate the blocking pattern of the compound on the transient outward current (Ito) in human subepicardial myocytes isolated from explanted left ventricles. Using the single electrode whole cell voltage clamp technique, Ito was analysed after appropriate voltage inactivation of sodium current and block of calcium current.Tedisamil reduced the amplitude of peak Ito, but did not affect the amplitude of non-inactivating outward current. The drug accelerated the apparent rate of Ito inactivation. The reduction in time constant of Ito inactivation depended on drug concentration, the apparent IC50 value was 4.4 μM.Tedisamil affected Ito amplitude in a use-dependent manner. After 2 min at −80 mV, maximum block of Ito was reached after 4–5 clamp steps either at the frequency of 0.2 or 2 Hz, indicating that the block was not frequency-dependent in an experimentally relevant range. Recovery from block was very slow and proceeded with a time constant of 12.1±1.8 s. Also in the presence of drug, a fraction of channels recovered from inactivation with a similar time constant as in control myocytes (i.e. 81±40 ms and 51±8 ms, respectively, n.s.).From the onset of fractional block of Ito by tedisamil during the initial 60 ms of a clamp step, we calculated k1=9×106 mol−1 s−1 for the association rate constant, and k2=23 s−1 for the dissociation rate constant. The resulting apparent KD was 2.6 μM and is similar to the IC50 value.The effects of tedisamil on Ito could be simulated by assuming a four state channel model where the drug binds to the channel in an open (activated) conformation. It is concluded that in human subepicardial myocytes tedisamil is an open channel blocker of Ito and that this effect probably contributes to the antiarrhythmic potential of this drug. PMID:9831899

Doppler-resolved kinetics of saturation recovery

DOE PAGES

Forthomme, Damien; Hause, Michael L.; Yu, Hua -Gen; ...

2015-04-08

Frequency modulated laser transient absorption has been used to monitor the ground state rotational energy transfer rates of CN radicals in a double-resonance, depletion recovery experiment. When a pulsed laser is used to burn a hole in the equilibrium ground state population of one rotational state without velocity selection, the population recovery rate is found to depend strongly on the Doppler detuning of a narrow-band probe laser. Similar effects should be apparent for any relaxation rate process that competes effectively with velocity randomization. Alternative methods of extracting thermal rate constants in the presence of these non-thermal conditions are evaluated. Totalmore » recovery rate constants, analogous to total removal rate constants in an experiment preparing a single initial rotational level, are in good agreement with quantum scattering calculations, but are slower than previously reported experiments and show qualitatively different rotational state dependence between Ar and He collision partners. As a result, quasi-classical trajectory studies confirm that the differing rotational state dependence is primarily a kinematic effect.« less

Energetics of sodium transport in toad urinary bladder.

PubMed Central

Canessa, M; Labarca, P; DiBona, D R; Leaf, A

1978-01-01

The ratio of the rate of transepithelial sodium transport, JNa, across the isolated toad urinary bladder to the simultaneously measured rate of transport-dependent metabolism, JsbCO2, has been measured as a function of the transepithelial electrical voltage, deltapsi. The ratio remains constant with a mean value of 18 to 20 over the range of imposed voltages of 0 to +70 mV. With increasing hyperpolarization of the bladder, JNa decreases and the calculated electromotive force or apparent "ENa" of the sodium pump increases. From thermodynamic and kinetic arguments it is shown that the apparent "ENa" approaches the maximal electrochemical potential gradient, ENa, against which sodium can be transported by this tissue only when JNa approximately 0. At this unique condition F ENa (in which F is the Faraday constant) is the maximal free energy of the chemical reaction driving sodium transport and thus equal to the maximal extramitochondrial phosphorylation potential and the maximal free energy of the mitochondrial respiratory chain within the transporting cells. PMID:100789

Mixing effects on apparent reaction rates and isotope fractionation during denitrification in a heterogeneous aquifer

USGS Publications Warehouse

Green, Christopher T.; Böhlke, John Karl; Bekins, Barbara A.; Phillips, Steven P.

2010-01-01

Gradients in contaminant concentrations and isotopic compositions commonly are used to derive reaction parameters for natural attenuation in aquifers. Differences between field‐scale (apparent) estimated reaction rates and isotopic fractionations and local‐scale (intrinsic) effects are poorly understood for complex natural systems. For a heterogeneous alluvial fan aquifer, numerical models and field observations were used to study the effects of physical heterogeneity on reaction parameter estimates. Field measurements included major ions, age tracers, stable isotopes, and dissolved gases. Parameters were estimated for the O2 reduction rate, denitrification rate, O2 threshold for denitrification, and stable N isotope fractionation during denitrification. For multiple geostatistical realizations of the aquifer, inverse modeling was used to establish reactive transport simulations that were consistent with field observations and served as a basis for numerical experiments to compare sample‐based estimates of “apparent” parameters with “true“ (intrinsic) values. For this aquifer, non‐Gaussian dispersion reduced the magnitudes of apparent reaction rates and isotope fractionations to a greater extent than Gaussian mixing alone. Apparent and true rate constants and fractionation parameters can differ by an order of magnitude or more, especially for samples subject to slow transport, long travel times, or rapid reactions. The effect of mixing on apparent N isotope fractionation potentially explains differences between previous laboratory and field estimates. Similarly, predicted effects on apparent O2threshold values for denitrification are consistent with previous reports of higher values in aquifers than in the laboratory. These results show that hydrogeological complexity substantially influences the interpretation and prediction of reactive transport.

Evaluation and comparison of diffusion MR methods for measuring apparent transcytolemmal water exchange rate constant

NASA Astrophysics Data System (ADS)

Tian, Xin; Li, Hua; Jiang, Xiaoyu; Xie, Jingping; Gore, John C.; Xu, Junzhong

2017-02-01

Two diffusion-based approaches, CG (constant gradient) and FEXI (filtered exchange imaging) methods, have been previously proposed for measuring transcytolemmal water exchange rate constant kin, but their accuracy and feasibility have not been comprehensively evaluated and compared. In this work, both computer simulations and cell experiments in vitro were performed to evaluate these two methods. Simulations were done with different cell diameters (5, 10, 20 μm), a broad range of kin values (0.02-30 s-1) and different SNR's, and simulated kin's were directly compared with the ground truth values. Human leukemia K562 cells were cultured and treated with saponin to selectively change cell transmembrane permeability. The agreement between measured kin's of both methods was also evaluated. The results suggest that, without noise, the CG method provides reasonably accurate estimation of kin especially when it is smaller than 10 s-1, which is in the typical physiological range of many biological tissues. However, although the FEXI method overestimates kin even with corrections for the effects of extracellular water fraction, it provides reasonable estimates with practical SNR's and more importantly, the fitted apparent exchange rate AXR showed approximately linear dependence on the ground truth kin. In conclusion, either CG or FEXI method provides a sensitive means to characterize the variations in transcytolemmal water exchange rate constant kin, although the accuracy and specificity is usually compromised. The non-imaging CG method provides more accurate estimation of kin, but limited to large volume-of-interest. Although the accuracy of FEXI is compromised with extracellular volume fraction, it is capable of spatially mapping kin in practice.

An experimental comparison of several current viscoplastic constitutive models at elevated temperature

NASA Technical Reports Server (NTRS)

James, G. H.; Imbrie, P. K.; Hill, P. S.; Allen, D. H.; Haisler, W. E.

1988-01-01

Four current viscoplastic models are compared experimentally for Inconel 718 at 593 C. This material system responds with apparent negative strain rate sensitivity, undergoes cyclic work softening, and is susceptible to low cycle fatigue. A series of tests were performed to create a data base from which to evaluate material constants. A method to evaluate the constants is developed which draws on common assumptions for this type of material, recent advances by other researchers, and iterative techniques. A complex history test, not used in calculating the constants, is then used to compare the predictive capabilities of the models. The combination of exponentially based inelastic strain rate equations and dynamic recovery is shown to model this material system with the greatest success. The method of constant calculation developed was successfully applied to the complex material response encountered. Backstress measuring tests were found to be invaluable and to warrant further development.

1H-NMR and Hyperpolarized 13C-NMR Assays of Pyruvate-Lactate Exhange: a comparative study

PubMed Central

Orton, Matthew R.; Tardif, Nicolas; Parkes, Harold G.; Robinson, Simon P.; Leach, Martin O.; Chung, Yuen-Li; Eykyn, Thomas R.

2015-01-01

Pyruvate-lactate exchange is mediated by the enzyme lactate dehydrogenase (LDH) and is central to the altered energy metabolism in cancer cells. Measurement of exchange kinetics using hyperpolarized 13C NMR has provided a biomarker of response to novel therapeutics. In this study we investigated an alternative in vitro 1H assay, using [3-13C]pyruvate, and compared the measured kinetics with a hyperpolarized 13C-NMR assay, using [1-13C]pyruvate, under the same conditions in human colorectal carcinoma SW1222 cells. The apparent forward reaction rate constants (kPL) derived from the two assays showed no significant difference, and both assays had similar reproducibility (kPL = 0.506 ± 0.054 and kPL = 0.441 ± 0.090 nmol/s/106 cells, (mean ± standard deviation, n = 3); 1H, 13C assays respectively). The apparent backward reaction rate constant (kLP) could only be measured with good reproducibility using the 1H-NMR assay (kLP = 0.376 ± 0.091 nmol/s/106 cells, (mean ± standard deviation, n = 3)). The 1H-NMR assay has adequate sensitivity to measure real-time pyruvate-lactate exchange kinetics in vitro, offering a complementary and accessible assay of apparent LDH activity. PMID:23712817

A laser flash photolysis-resonance fluorescence kinetics study of the reaction Cl/2P/ + CH4 yields CH3 + HCl

NASA Technical Reports Server (NTRS)

Ravishankara, A. R.; Wine, P. H.

1980-01-01

The technique of laser flash photolysis-resonance fluorescence is employed to study the kinetics of the reaction Cl(2P) + CH4 yields CH3 + HCl over the temperature range 221-375 K. At temperatures less than or equal to 241 K the apparent bimolecular rate constant is found to be dependent upon the identity of the chemically inert gases in the reaction mixture. For Cl2/CH4/He reaction mixtures (total pressure = 50 torr) different bimolecular rate constants are measured at low and high methane concentrations. For Cl2/CH4/CCl/He and Cl2/CH4/Ar reaction mixtures, the bimolecular rate constant is independent of methane concentration, being approximately equal to the rate constant measured at low methane concentrations for Cl2/CH4/He mixtures. These rate constants are in good agreement with previous results obtained using the discharge flow-resonance fluorescence and competitive chlorination techniques. At 298 K the measured bimolecular rate constant is independent of the identity of the chemically inert gases in the reaction mixture and in good agreement with all previous investigations. The low-temperature results obtained in this investigation and all previous investigations can be rationalized in terms of a model which assumes that the Cl(2P 1/2) state reacts with CH4 much faster than the Cl(2P 3/2) state. Extrapolation of this model to higher temperatures, however, is not straightforward.

Fractional time-dependent apparent viscosity model for semisolid foodstuffs

NASA Astrophysics Data System (ADS)

Yang, Xu; Chen, Wen; Sun, HongGuang

2017-10-01

The difficulty in the description of thixotropic behaviors in semisolid foodstuffs is the time dependent nature of apparent viscosity under constant shear rate. In this study, we propose a novel theoretical model via fractional derivative to address the high demand by industries. The present model adopts the critical parameter of fractional derivative order α to describe the corresponding time-dependent thixotropic behavior. More interestingly, the parameter α provides a quantitative insight into discriminating foodstuffs. With the re-exploration of three groups of experimental data (tehineh, balangu, and natillas), the proposed methodology is validated in good applicability and efficiency. The results show that the present fractional apparent viscosity model performs successfully for tested foodstuffs in the shear rate range of 50-150 s^{ - 1}. The fractional order α decreases with the increase of temperature at low temperature, below 50 °C, but increases with growing shear rate. While the ideal initial viscosity k decreases with the increase of temperature, shear rate, and ingredient content. It is observed that the magnitude of α is capable of characterizing the thixotropy of semisolid foodstuffs.

Measurement of the steady-state shear characteristics of filamentous suspensions using turbine, vane, and helical impellers.

PubMed

Svihla, C K; Dronawat, S N; Donnelly, J A; Rieth, T C; Hanley, T R

1997-01-01

The impeller viscometer technique is frequently used to characterize the rheology of filamentous suspensions in order to avoid difficulties encountered with conventional instruments. This work presents the results of experiments conducted with vane, turbine, and helical impellers. The validity of the assumptions made in the determination of the torque and shear-rate constants were assessed for each impeller type. For the turbine and vane impellers, an increase in the apparent torque constant c was observed with increasing Reynolds number even when measurements were confined to the viscous regime. The shear-rate constants determined for the vane and turbine impellers varied for different calibration fluids, which contradicts the assumptions usually invoked in the analysis of data for this technique. When the helical impeller was calibrated, consistent values for the torque and shear-rate constants were obtained. The three impeller types were also used to characterize the rheology of cellulose fiber suspensions and the results compared for consistency and reproducibility. The results have application in design of rheometers for use in process control and product quality assessment in the fermentation and pulp and paper industries.

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

Vargas, Ronald; Nunez, Oswaldo

Photodegradation/mineralization (TiO{sub 2}/UV Light) of the hydrocarbons: p-nitrophenol (PNP), naphthalene (NP) and dibenzothiophene (DBT) at three different reactors: batch bench reactor (BBR), tubular bench reactor (TBR) and tubular pilot-plant (TPP) were kinetically monitored at pH = 3, 6 and 10, and the results compared using normalized UV light exposition times. The results fit the Langmuir-Hinshelwood (LH) model; therefore, LH adsorption equilibrium constants (K) and apparent rate constants (k) are reported as well as the apparent pseudo-first-order rate constants, k{sub obs}{sup '} = kK/(1 + Kc{sub r}). The batch bench reactor is the most selective reactor toward compound and pH changesmore » in which the reactivity order is: NP > DBT > PNP, however, the catalyst adsorption (K) order is: DBT > NP > PNP at the three pH used but NP has the highest k values. The tubular pilot-plant (TPP) is the most efficient of the three reactors tested. Compound and pH photodegradation/mineralization selectivity is partially lost at the pilot plant where DBT and NP reaches ca. 90% mineralization at the pH used, meanwhile, PNP reaches only 40%. The real time, in which these mineralization occur are: 180 min for PNP and 60 min for NP and DBT. The mineralization results at the TPP indicate that for the three compounds, the rate limiting step is the same as the degradation one. So that, there is not any stable intermediate that may accumulate during the photocatalytic treatment. (author)« less

Phosphatidylglycerol synthesis in castor bean endosperm. [Ricinus communis

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

Moore, T.S. Jr.

1974-01-01

The synthesis of phosphatidylglycerol in castor bean (Ricinus communis var. Hale) endosperm tissue was found to be located in both the endoplasmic reticulum and mitochondrial fractions separated on sucrose density gradients. The enzyme of both fractions attained maximum activity at 5 mM Mn/sup 2 +/, 0.075 percent Triton X-100, and pH 7.3. The addition of dithiothreitol produced little effect, but sulfhydryl inhibitors reduced activity in both systems. Cytidine diphosphate-diglyceride exhibited an apparent Michaelis constant for the endoplasmic reticulum enzyme of 2.8 ..mu..M and for the mitochondrial enzyme of 2.0 ..mu..M; the maximum reaction rate was achieved at about 20 ..mu..M.more » For the second substrate, glycerol-phosphate, the apparent Michaelis constant for both fractions was about 50 ..mu..M and maximum velocity was reached at 400 ..mu..M. The specific activity of the mitochondrial enzyme was generally twice that of the endoplasmic reticulum.« less

Determination of acidity and nucleophilicity in thiols by reaction with monobromobimane and fluorescence detection.

PubMed

Sardi, Florencia; Manta, Bruno; Portillo-Ledesma, Stephanie; Knoops, Bernard; Comini, Marcelo A; Ferrer-Sueta, Gerardo

2013-04-01

A method based on the differential reactivity of thiol and thiolate with monobromobimane (mBBr) has been developed to measure nucleophilicity and acidity of protein and low-molecular-weight thiols. Nucleophilicity of the thiolate is measured as the pH-independent second-order rate constant of its reaction with mBBr. The ionization constants of the thiols are obtained through the pH dependence of either second-order rate constant or initial rate of reaction. For readily available thiols, the apparent second-order rate constant is measured at different pHs and then plotted and fitted to an appropriate pH function describing the observed number of ionization equilibria. For less available thiols, such as protein thiols, the initial rate of reaction is determined in a wide range of pHs and fitted to the appropriate pH function. The method presented here shows excellent sensitivity, allowing the use of nanomolar concentrations of reagents. The method is suitable for scaling and high-throughput screening. Example determinations of nucleophilicity and pK(a) are presented for captopril and cysteine as low-molecular-weight thiols and for human peroxiredoxin 5 and Trypanosoma brucei monothiol glutaredoxin 1 as protein thiols. Copyright © 2013 Elsevier Inc. All rights reserved.

Clay catalysis of oligonucleotide formation: kinetics of the reaction of the 5'-phosphorimidazolides of nucleotides with the non-basic heterocycles uracil and hypoxanthine

NASA Technical Reports Server (NTRS)

Kawamura, K.; Ferris, J. P.

1999-01-01

The montmorillonite clay catalyzed condensation of activated monocleotides to oligomers of RNA is a possible first step in the formation of the proposed RNA world. The rate constants for the condensation of the phosphorimidazolide of adenosine were measured previously and these studies have been extended to the phosphorimidazolides of inosine and uridine in the present work to determine of substitution of neutral heterocycles for the basic adenine ring changes the reaction rate or regioselectivity. The oligomerization reactions of the 5'-phosphoromidazolides of uridine (ImpU) and inosine (ImpI) on montmorillonite yield oligo(U)s and oligo(I)s as long as heptamers. The rate constants for oligonucleotide formation were determined by measuring the rates of formation of the oligomers by HPLC. Both the apparent rate constants in the reaction mixture and the rate constants on the clay surface were calculated using the partition coefficients of the oligomers between the aqueous and clay phases. The rate constants for trimer formation are much greater than those dimer synthesis but there was little difference in the rate constants for the formation of trimers and higher oligomers. The overall rates of oligomerization of the phosphorimidazolides of purine and pyrimidine nucleosides in the presence of montmorillonite clay are the same suggesting that RNA formed on the primitive Earth could have contained a variety of heterocyclic bases. The rate constants for oligomerization of pyrimidine nucleotides on the clay surface are significantly higher than those of purine nucleotides since the pyrimidine nucleotides bind less strongly to the clay than do the purine nucleotides. The differences in the binding is probably due to Van der Waals interactions between the purine bases and the clay surface. Differences in the basicity of the heterocyclic ring in the nucleotide have little effect on the oligomerization process.

Erratum: Erratum to: Thermodynamic implications of the gravitationally induced particle creation scenario

NASA Astrophysics Data System (ADS)

Saha, Subhajit; Mondal, Anindita

2018-04-01

We would like to rectify an error regarding the validity of the first law of thermodynamics (FLT) on the apparent horizon of a spatially flat Friedmann-Lemaitre-Robertson-Walker (FLRW) universe for the gravitationally induced particle creation scenario with constant specific entropy and an arbitrary particle creation rate (see Sect. 3.1 of original article)

Influence of mass transfer resistance on overall nitrate removal rate in upflow sludge bed reactors.

PubMed

Ting, Wen-Huei; Huang, Ju-Sheng

2006-09-01

A kinetic model with intrinsic reaction kinetics and a simplified model with apparent reaction kinetics for denitrification in upflow sludge bed (USB) reactors were proposed. USB-reactor performance data with and without sludge wasting were also obtained for model verification. An independent batch study showed that the apparent kinetic constants k' did not differ from the intrinsic k but the apparent Ks' was significantly larger than the intrinsic Ks suggesting that the intra-granule mass transfer resistance can be modeled by changes in Ks. Calculations of the overall effectiveness factor, Thiele modulus, and Biot number combined with parametric sensitivity analysis showed that the influence of internal mass transfer resistance on the overall nitrate removal rate in USB reactors is more significant than the external mass transfer resistance. The simulated residual nitrate concentrations using the simplified model were in good agreement with the experimental data; the simulated results using the simplified model were also close to those using the kinetic model. Accordingly, the simplified model adequately described the overall nitrate removal rate and can be used for process design.

Effect of solvent on crystallization behavior of xylitol

NASA Astrophysics Data System (ADS)

Hao, Hongxun; Hou, Baohong; Wang, Jing-Kang; Lin, Guangyu

2006-04-01

Effect of organic solvents content on crystallization behavior of xylitol was studied. Solubility and crystallization kinetics of xylitol in methanol-water system were experimentally determined. It was found that the solubility of xylitol at various methanol content all increases with increase of temperature. But it decreases when increasing methanol content at constant temperature. Based on the theory of population balance, the nucleation and growth rates of xylitol in methanol-water mixed solvents were calculated by moments method. From a series of experimental population density data of xylitol gotten from a batch-operated crystallizer, parameters of crystal nucleation and growth rate equations at different methanol content were got by the method of nonlinear least-squares. By analyzing, it was found that the content of methanol had an apparent effect on nucleation and growth rate of xylitol. At constant temperature, the nucleation and growth rate of xylitol all decrease with increase of methanol content.

Kinetics and mechanism of hydroxyapatite crystal dissolution in weak acid buffers using the rotating disk method.

PubMed

Wu, M S; Higuchi, W I; Fox, J L; Friedman, M

1976-01-01

The model given in this report and the rotating disk method provide a useful combination in the study of dental enamel and hydroxyapatite dissolution kinetics. The present approach is a significant improvement over earlier studies, and both the ionic activity product that governs the dissolution reaction and the apparent surface dissolution reaction rate constant may be simultaneously obtained. Thus, these investigations have established the baseline for the dissolution rate studies under sink conditions. Concurrent studies, under conditions where the acidic buffer mediums are partially saturated with respect to hydroxyapatite have shown another dissolution site for hydroxyapatite that operates at a higher ionic activity product but has a much smaller apparent surface reaction rate constant. This has raised the question of whether the presence of this second site may interfere with the proper theoretical analysis of the experimental results obtained under sink conditions. A preliminary analysis of the two-site model has shown that the dissolution kinetics of hydroxyapatite under sink conditions is almost completely governed by the sink condition site (KHAP = 10(-124.5), k' = 174) established in this report. The difference between the predicted dissolution rate for the one-site model and the two-site model are generally of the order of 4 to 5% where the experiments are conducted under sink conditions and over the range of variables covered in the present study.

Scale-Dependent Rates of Uranyl Surface Complexation Reaction in Sediments

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

Liu, Chongxuan; Shang, Jianying; Kerisit, Sebastien N.

Scale-dependency of uranyl[U(VI)] surface complexation rates was investigated in stirred flow-cell and column systems using a U(VI)-contaminated sediment from the US Department of Energy, Hanford site, WA. The experimental results were used to estimate the apparent rate of U(VI) surface complexation at the grain-scale and in porous media. Numerical simulations using molecular, pore-scale, and continuum models were performed to provide insights into and to estimate the rate constants of U(VI) surface complexation at the different scales. The results showed that the grain-scale rate constant of U(VI) surface complexation was over 3 to 10 orders of magnitude smaller, dependent on themore » temporal scale, than the rate constant calculated using the molecular simulations. The grain-scale rate was faster initially and slower with time, showing the temporal scale-dependency. The largest rate constant at the grain-scale decreased additional 2 orders of magnitude when the rate was scaled to the porous media in the column. The scaling effect from the grain-scale to the porous media became less important for the slower sorption sites. Pore-scale simulations revealed the importance of coupled mass transport and reactions in both intragranular and inter-granular domains, which caused both spatial and temporal dependence of U(VI) surface complexation rates in the sediment. Pore-scale simulations also revealed a new rate-limiting mechanism in the intragranular porous domains that the rate of coupled diffusion and surface complexation reaction was slower than either process alone. The results provided important implications for developing models to scale geochemical/biogeochemical reactions.« less

Carbohydrate Partitioning and the Capacity of Apparent Nitrogen Fixation of Soybean Plants Grown Outdoors

PubMed Central

Millhollon, Eddie P.; Williams, Larry E.

1986-01-01

Patterns of leaf carbohydrate partitioning and nodule activity in soybean plants grown under natural conditions and the irradiance level required to produce sufficient carbohydrate to obtain maximum rates of apparent N2-fixation (acetylene reduction) were measured. Soybean plants, grown outdoors, maintained constant levels of leaf soluble sugars while leaf starch pools varied diurnally. When root temperature was kept at 25°C and shoot temperature was allowed to vary with ambient temperature, the plants maintained constant rates of apparent N2-fixation and root+nodule respiration. Results from a second experiment, in which the entire plant was kept at 25°C, were similar to those of the first experiment. Shoot carbon exchange rate of plants from the second experiment was light saturated at photosynthetic photon flux densities between 400 and 600 micromoles per square meter per second. When plants were subjected to an extended 40-hour dark period to deplete carbohydrate reserves, apparent N2-fixation was unaffected during the first 10 hours of darkness, decreased rapidly between 10 and 16 hours, and plateaued at one-third the initial level thereafter. After the extended dark period, plants were exposed to photosynthetic photon flux density from 200 to 1000 micromoles per square meter per second for 10 hours. Photosynthetic photon flux densities of 200 micromoles per square meter per second and greater resulted in maximum leaf soluble sugar content and nodule activity. Leaf starch content increased with irradiance levels up to 600 micromoles per square meter per second with no further increase at higher irradiance levels. Results presented here indicate that maximum nodule activity occurs at irradiance levels that do not saturate the plant's photosynthetic apparatus. This response would allow for maximum N2-fixation to occur in a nodulated legume during periods of inclement weather. PMID:16664789

Photolysis of 2,4,6-trinitrotoluene in seawater and estuary water: Impact of pH, temperature, salinity, and dissolved organic matter.

PubMed

Luning Prak, Dianne J; Breuer, James E T; Rios, Evelyn A; Jedlicka, Erin E; O'Sullivan, Daniel W

2017-01-30

The influence of salinity, pH, temperature, and dissolved organic matter on the photolysis rate of 2,4,6-trinitrotoluene (TNT) in marine, estuary, and laboratory-prepared waters was studied using a Suntest CPS+® solar simulator equipped with optical filters. TNT degradation rates were determined using HPLC analysis, and products were identified using LC/MS. Minimal or no TNT photolysis occurred under a 395-nm long pass filter, but under a 295-nm filter, first-order TNT degradation rate constants and apparent quantum yields increased with increasing salinity in both natural and artificial seawater. TNT rate constants increased slightly with increasing temperature (10 to 32°C) but did not change significantly with pH (6.4 to 8.1). The addition of dissolved organic matter (up to 5mg/L) to ultrapure water, artificial seawater, and natural seawater increased the TNT photolysis rate constant. Products formed by TNT photolysis in natural seawater were determined to be 2,4,6-trinitrobenzaldehyde, 1,3,5-trinitrobenzene, 2,4,6-trinitrobenzoic acid, and 2-amino-4,6-dinitrobenzoic acid. Published by Elsevier Ltd.

Nano-Advantage in Enhanced Drug Delivery with Biodegradable Nanoparticles: Contribution of Reduced Clearance

PubMed Central

Kadam, Rajendra S.; Bourne, David W. A.

2012-01-01

The aim of this study was to investigate the contribution of reduced apparent clearance to the enhanced exposure reported for biodegradable nanoparticles after extravascular and intravascular routes of administration. Plasma concentration profiles for drug and nanoparticle formulations after administration by intravenous, intraduodenal, and oral routes were extracted from the literature. Data were fit to pharmacokinetic models using BOOMER. The compartmental pharmacokinetic analysis of literature data for six drugs (camptothecin, 9-nitrocamptothecin, epirubicin, vinpocetine, clozapine, and cyclosporine) showed that the encapsulation of drug molecules in nanoparticles significantly reduced the apparent clearance and prolonged the apparent circulation half-life compared with those for the plain drug. Positively charged nanoparticles assessed in this study had lower apparent clearance, lower elimination rate constant values, and longer apparent circulation half-life than neutral and negatively charged nanoparticles. After oral administration, a reduction in apparent clearance contributed substantially to elevations in plasma drug exposure with nanoparticles. For the drugs and delivery systems examined, the nano-advantage in drug delivery enhancement can be explained, in part, by reduced clearance. PMID:22498894

Crack deflection: Implications for the growth of long and short fatigue cracks

NASA Astrophysics Data System (ADS)

Suresh, S.

1983-11-01

The influences of crack deflection on the growth rates of nominally Mode I fatigue cracks are examined. Previous theoretical analyses of stress intensity solutions for kinked elastic cracks are reviewed. Simple elastic deflection models are developed to estimate the growth rates of nonlinear fatigue cracks subjected to various degrees of deflection, by incorporating changes in the effective driving force and in the apparent propagation rates. Experimental data are presented for intermediate-quenched and step-quenched conditions of Fe/2Si/0.1C ferrite-martensite dual phase steel, where variations in crack morphology alone influence considerably the fatigue crack propagation rates and threshold stress intensity range values. Such results are found to be in good quantitative agreement with the deflection model predictions of propagation rates for nonlinear cracks. Experimental information on crack deflection, induced by variable amplitude loading, is also provided for 2020-T651 aluminum alloy. It is demonstrated with the aid of elastic analyses and experiments that crack deflection models offer a physically-appealing rationale for the apparently slower growth rates of long fatigue cracks subjected to constant and variable amplitude loading and for the apparent deceleration and/or arrest of short cracks. The changes in the propagation rates of deflected fatigue cracks are discussed in terms of the local mode of crack advance, microstructure, effective driving force, growth mechanisms, mean stress, slip characteristics, and crack closure.

Photosynthesis: Action Spectra for Leaves in Normal and Low Oxygen 1

PubMed Central

Bulley, N. R.; Nelson, C. D.; Tregunna, E. B.

1969-01-01

The action spectrum of apparent photosynthesis for attached radish (Raphanus sativus L. var. Early Scarlet Globe) and corn (Zea mays L. var. Pride V.) leaves was measured at 300 μl/l CO2 and both 21% and 2% O2. The spectra were measured at light intensities where apparent photosynthesis was proportional to intensity. For radish, a high compensation point plant, oxygen had an inhibiting effect on photosynthesis at all wavelengths from 402 to 694 mμ. If a constant rate of photosynthesis at 21% O2 for the different wavelengths was chosen, then the percent increase in net CO2 fixation at 2% O2 was constant. For corn, a low compensation point plant, no inhibitory effect of oxygen concentration from 2% to 21% O2 was found over the visible spectrum. The CO2 compensation point for light intensities greater than the light compensation point was found to be constant and independent of wavelength for both radish and corn leaves. For radish, the lowering of the oxygen concentration from 21% to 2% at these intensities was found to reduce the CO2 compensation point by the same amount for the wavelengths studied. PMID:16657120

Evaluation of the apparent phytodegradation of pentachlorophenol by Chlorella pyrenoidosa.

PubMed

Headley, John V; Peru, Kerry M; Du, Jing-Long; Gurprasad, Narine; McMartin, Dena W

2008-03-01

Several factors influencing the apparent phytodegradation of pentachlorophenol (PCP) were investigated under controlled laboratory conditions including photolysis, biodegradation, and direct phytodegradation by the algae, Chlorella pyrenoidosa. PCP was observed to degrade over time in all instances. Degradation occurred both with and without the presence of algae. The degradation of PCP was observed to be dependent primarily on photolysis with pseudo-first-order kinetics and rate constants in the range of 6.4 to 7.7 h(-1). In contrast, phytodegradation due to algal activity was negligible. It is suspected that the algae degradation may have been limited by the cycling of light exposure to simulate day and night periods.

Diffusional falsification of kinetic constants on Lineweaver-Burk plots.

PubMed

Ghim, Y S; Chang, H N

1983-11-07

The effect of mass transfer resistances on the Lineweaver-Burk plots in immobilized enzyme systems has been investigated numerically and with analytical approximate solutions. While Hamilton, Gardner & Colton (1974) studied the effect of internal diffusion resistances in planar geometry, our study was extended to the combined effect of internal and external diffusion in cylindrical and spherical geometries as well. The variation of Lineweaver-Burk plots with respect to the geometries was minimized by modifying the Thiele modulus and the Biot number with the shape factor. Especially for a small Biot number all the three Lineweaver-Burk plots fell on a single line. As was discussed by Hamilton et al. (1974), the curvature of the line for large external diffusion resistances was small enough to be assumed linear, which was confirmed from the two approximate solutions for large and small substrate concentrations. Two methods for obtaining intrinsic kinetic constants were proposed: First, we obtained both maximum reaction rate and Michaelis constant by fitting experimental data to a straight line where external diffusion resistance was relatively large, and second, we obtained Michaelis constant from apparent Michaelis constant from the figure in case we knew maximum reaction rate a priori.

Enhanced sonochemical degradation of azure B dye by the electroFenton process.

PubMed

Martínez, Susana Silva; Uribe, Edgar Velasco

2012-01-01

The degradation of azure B dye (C15H16ClN3S; AB) has been studied by Fenton, sonolysis and sono-electroFenton processes employing ultrasound at 23 kHz and the electrogeneration of H2O2 at the reticulated vitreous carbon electrode. It was found that the dye degradation followed apparent first-order kinetics in all the degradation processes tested. The rate constant was affected by both the pH of the solution and initial concentration of Fe2+, with the highest degradation obtained at pH between 2.6 and 3. The first-order rate constant decreased in the following order: sono-electroFenton>Fenton>sonolysis. The rate constant for AB degradation by sono-electroFenton is ∼10-fold that of sonolysis and ∼2-fold the one obtained by Fenton under silent conditions. The chemical oxygen demand was abated ∼68% and ∼85% by Fenton and sono-electroFenton respectively, achieving AB concentration removal over 90% with both processes. Copyright © 2011 Elsevier B.V. All rights reserved.

Effects of multi-frequency power ultrasound on the enzymolysis of corn gluten meal: Kinetics and thermodynamics study.

PubMed

Jin, Jian; Ma, Haile; Qu, Wenjuan; Wang, Kai; Zhou, Cunshan; He, Ronghai; Luo, Lin; Owusu, John

2015-11-01

The effects of multi-frequency power ultrasound (MPU) pretreatment on the kinetics and thermodynamics of corn gluten meal (CGM) were investigated in this research. The apparent constant (KM), apparent break-down rate constant (kA), reaction rate constants (k), energy of activation (Ea), enthalpy of activation (ΔH), entropy of activation (ΔS) and Gibbs free energy of activation (ΔG) were determined by means of the Michaelis-Menten equation, first-order kinetics model, Arrhenius equation and transition state theory, respectively. The results showed that MPU pretreatment can accelerate the enzymolysis of CGM under different enzymolysis conditions, viz. substrate concentration, enzyme concentration, pH, and temperature. Kinetics analysis revealed that MPU pretreatment decreased the KM value by 26.1% and increased the kA value by 7.3%, indicating ultrasound pretreatment increased the affinity between enzyme and substrate. In addition, the values of k for ultrasound pretreatment were increased by 84.8%, 41.9%, 28.9%, and 18.8% at the temperature of 293, 303, 313 and 323 K, respectively. For the thermodynamic parameters, ultrasound decreased Ea, ΔH and ΔS by 23.0%, 24.3% and 25.3%, respectively, but ultrasound had little change in ΔG value in the temperature range of 293-323 K. In conclusion, MPU pretreatment could remarkably enhance the enzymolysis of CGM, and this method can be applied to protein proteolysis industry to produce peptides. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of drug lipophilicity on in vitro release rate from oil vehicles using nicotinic acid esters as model prodrug derivatives.

PubMed

Weng Larsen, S; Engelbrecht Thomsen, A E; Rinvar, E; Friis, G J; Larsen, C

2001-03-23

The rate constants for transfer of a homologous series of nicotinic acid esters from oil vehicles to aqueous buffer phases were determined using a rotating dialysis cell. The chemical stability of butyl nicotinate has been investigated at 60 degrees C over pH range 0.5--10. Maximum stability occurs at pH 4--5 and an inflection point was seen around the pK(a). For the nicotinic acid esters, a linear correlation was established between the first-order rate constant related to attainment of equilibrium, k(obs) and the apparent partition coefficient, P(app): log k(obs)=-0.83log P(app)+0.26 (k(obs) in h(-1), n=9). For hexyl nicotinate with a true partition coefficient of 4 it was possible to determine k(obs) by decreasing pH in the aqueous release medium to 2.05. Thus, under the latter experimental conditions estimation of the relative release rates for the esters were performed. The ratio between the specific rate constant k(ow), related to the transport from oil vehicle to aqueous phase, for ethyl and hexyl nicotinate was 139. The hydrophobic substituent constant for a methylene group, pi(CH(2)), was determined for nicotinic acid esters in different oil/buffer partitioning systems to 0.54--0.58. Addition of hydroxypropyl-beta-cyclodextrin to the aqueous release medium did not enhance the transport rate of the esters from the oil phase.

Kinetics and equilibria of cyanide binding to prostaglandin H synthase.

PubMed

MacDonald, I D; Dunford, H B

1989-09-01

Cyanide binding to prostaglandin H (PGH) synthase results in a spectral shift in the Soret region. This shift was exploited to determine equilibrium and kinetic parameters of the cyanide binding process. At pH 8.0, ionic strength 0.22 M, 4 degrees C, the cyanide dissociation constant, determined from equilibrium experiments, is (65 +/- 10) microM. The binding rate constant is (2.8 +/- 0.2) x 10(3) M-1 s-1, and the dissociation rate constant is zero within experimental error. Through a kinetic study of the binding process as a function of pH, from pH 3.96 to 8.00, it was possible to determine the pKa of a heme-linked acid group on the enzyme of 4.15 +/- 0.10 with citrate buffer. An apparent pKa of 4.75 +/- 0.03 was determined with acetate buffer; this different value is attributed to complexation of the enzyme with one of the components of the acetate buffer.

Implementation of steady state approximation for modelling of reaction kinetic of UV catalysed hydrogen peroxide oxidation of starch

NASA Astrophysics Data System (ADS)

Kumoro, Andri Cahyo; Retnowati, Diah Susetyo; Ratnawati, Budiyati, Catarina Sri

2015-12-01

With regard to its low viscosity, high stability, clarity, film forming and binding properties, oxidised starch has been widely used in various applications specifically in the food, paper, textile, laundry finishing and binding materials industries. A number of methods have been used to produce oxidised starch through reactions with various oxidizing agents, such as hydrogen peroxide, air oxygen, ozone, bromine, chromic acid, permanganate, nitrogen dioxide and hypochlorite. Unfortunately, most of previous works reported in the literatures were focused on the study of reaction mechanism and physicochemical properties characterization of the oxidised starches produced without investigation of the reaction kinetics of the oxidation process. This work aimed to develop a simple kinetic model for UV catalysed hydrogen peroxide oxidation of starch through implementation of steady state approximation for the radical reaction rates. The model was then verified using experimental data available in the literature. The model verification revealed that the proposed model shows its good agreement with the experimental data as indicated by an average absolute relative error of only 2.45%. The model also confirmed that carboxyl groups are oxidised further by hydroxyl radical. The carbonyl production rate was found to follow first order reaction with respect to carbonyl concentration. Similarly, carboxyl production rate also followed first order reaction with respect to carbonyl concentration. The apparent reaction rate constant for carbonyl formation and oxidation were 6.24 × 104 s-1 and 1.01 × 104 M-1.s-1, respectively. While apparent reaction rate constant for carboxyl oxidation was 4.86 × 104 M-1.s-1.

Kinetics of copper ion absorption by cross-linked calcium polyacrylate membranes

NASA Technical Reports Server (NTRS)

Philipp, W. H.; May, C. E.

1983-01-01

The absorption of copper ions from aqueous copper acetate solutions by cross-linked calcium acrylate membranes was found to obey parabolic kinetics similar to that found for oxidation of metals that form protective oxide layers. For pure calcium polyacrylate membranes the rate constant was essentially independent of copper acetate concentration and film thickness. For a cross-linked copolymer film of polyvinyl alcohol and calcium polyacrylate, the rate constant was much greater and dependent on the concentration of copper acetate. The proposed mechanism in each case involves the formation of a copper polyacrylate phase on the surface of the membrane. The diffusion of the copper ion through this phase appears to be the rate controlling step for the copolymer film. The diffusion of the calcium ion is apparently the rate controlling step for the calcium polyacrylate. At low pH, the copper polyacrylate phase consists of the normal copper salt; at higher pH, the phase appears to be the basic copper salt.

Voltage dependence of acetylcholine receptor channel gating in rat myoballs

PubMed Central

1992-01-01

Whole-cell currents from nicotinic acetylcholine receptor (AChR) channels were studied in rat myoballs using a light-activated agonist to determine the voltage dependence of the macroscopic opening and closing rate constants. Myoballs were bathed in a solution containing a low concentration of the inactive isomer of the photoisomerizable azobenzene derivative, cis-Bis-Q. A light flash was then presented to produce a known concentration jump of agonist, trans-Bis-Q, across a wide range of membrane potentials in symmetrical solutions (NaCl or CsCl on both sides) or asymmetrical solutions (NaCl in the bath and CsCl in the pipette). At the low agonist concentration used in this study, the reciprocal of the macroscopic time constants gives an unambiguous measure of the effective closing rate. It showed an exponential decrease with membrane hyperpolarization between +20 and - 100 mV, but tended to level off at more depolarized and at more hyperpolarized membrane potentials. The relative effective opening rate was derived from the steady-state conductance, the single-channel conductance, and the apparent closing rate; it decreased sharply in the depolarizing region and tended to level off and then turn up in the hyperpolarizing region. The two effective rate constants were shown to depend on the first, second, and third power of membrane potential. PMID:1460456

Liquid-Phase Heat-Release Rates of the Systems Hydrazine-Nitric Acid and Unsymmetrical Dimethylhydrazine-Nitric Acid

NASA Technical Reports Server (NTRS)

Somogyi, Dezso; Feiler, Charles E.

1960-01-01

The initial rates of heat release produced by the reactions of hydrazine and unsymmetrical dimethylhydrazine with nitric acid were determined in a bomb calorimeter under conditions of forced mixing. Fuel-oxidant weight ratio and injection velocity were varied. The rate of heat release apparently depended on the interfacial area between the propellants. Above a narrow range of injection velocities representing a critical amount of interfacial area, the rates reached a maximum and were almost constant with injection velocity. The maximum rate for hydrazine was about 70 percent greater than that for unsymmetrical dimethylhydrazine. The total heat released did not vary with mixture ratio over the range studied.

Seedless synthesis and efficient recyclable catalytic activity of Ag@Fe nanocomposites towards methyl orange

NASA Astrophysics Data System (ADS)

Alzahrani, Salma Ahmed; Malik, Maqsood Ahmad; Al-Thabaiti, Shaeel Ahmed; Khan, Zaheer

2018-03-01

This work demonstrates a competitive reduction method of synthesis of nanomaterials. In this method along cetyltrimethylammonium bromide (CTAB), the reduction of Ag+ and Fe3+ ions is achieved by ascorbic acid-to-bimetallic Ag@Fe yellow-colored nanomaterials. The shape of UV-visible spectra and wavelengths absorbed of Ag@Fe can be tuned from ca. 290-600 nm by controlling [CTAB] and [Ag+]. The apparent first-order rate constants were calculated within the approximation of 6.1 × 10-3 s-1. The as-prepared Ag@Fe NPs have been found to be very important catalyst in terms of depredate methyl orange in vicinity of sodium borohydride (NaBH4), which exhibits excellent efficiency and re-usability in the prototypical reaction. The cmc of cationic surfactant CTAB has been determined by conductivity method under different experimental conditions. In the presence of CTAB, Ag+ and Fe3+ ions reduce to Ag@Fe core/shell nanoparticles, comprehend a change in wavelength and intensity of SRP band. The apparent first-order rate constant, activation energy, and turnover frequency for the methyl orange reduction catalyzed by Ag@Fe NPs were found to be 1.6 × 10-3 s-1, 58.2 kJ mol-1, and 1.1 × 10-3 s-1, respectively.

Study of the sonophotocatalytic degradation of basic blue 9 industrial textile dye over slurry titanium dioxide and influencing factors.

PubMed

González, Antonia Sandoval; Martínez, Susana Silva

2008-09-01

The sonophotocatalytic degradation of basic blue 9 industrial textile dye has been studied in the presence of ultrasound (20 kHz) over a TiO(2) slurry employing an UV lamp (15 W, 352 nm). It was observed that the color removal efficiency was influenced by the pH of the solution, initial dye concentration and TiO(2) amount. It was found that the dye degradation followed apparent first order kinetics. The rate constant increased by decreasing dye concentration and was affected by the pH of the solution with the highest degradation obtained at pH 7. The first order rate constants obtained with sonophotocatalysis were twofold and tenfold than those obtained under photocatalysis and sonolysis, respectively. The chemical oxygen demand was abated over 80%.

Modelling bioaccumulation of semi-volatile organic compounds (SOCs) from air in plants based on allometric principles.

PubMed

Steyaert, Nils L L; Hauck, Mara; Van Hulle, Stijn W H; Hendriks, A Jan

2009-10-01

A model was developed for gaseous plant-air exchange of semi-volatile organic compounds. Based on previous soil-plant modelling, uptake and elimination kinetics were scaled as a function of plant mass and octanol-air partition ratios. Exchange of chemicals was assumed to be limited by resistances encountered during diffusion through a laminar boundary layer of air and permeation through the cuticle of the leaf. The uptake rate constant increased and the elimination rate constant decreased with the octanol-air partition ratio both apparently levelling off at high values. Differences in kinetics between species could be explained by their masses. Validation on independent data showed that bio-concentration factors of PCBs, chlorobenzenes and other chemicals were predicted well by the model. For pesticides, polycyclic aromatic hydrocarbons and dioxins deviations occurred.

Intracellular diffusion in the presence of mobile buffers. Application to proton movement in muscle.

PubMed

Irving, M; Maylie, J; Sizto, N L; Chandler, W K

1990-04-01

Junge and McLaughlin (1987) derived an expression for the apparent diffusion constant of protons in the presence of both mobile and immobile buffers. Their derivation applies only to cases in which the values of pH are considerably greater than the largest pK of the individual buffers, a condition that is not expected to hold in skeletal muscle or many other cell types. Here we show that, if the pH gradients are small, the same expression for the apparent diffusion constant of protons can be derived without such constraints on the values of the pK's. The derivation is general and can be used to estimate the apparent diffusion constant of any substance that diffuses in the presence of both mobile and immobile buffers. The apparent diffusion constant of protons is estimated to be 1-2 x 10(-6) cm2/s at 18 degrees C inside intact frog twitch muscle fibers. It may be smaller inside cut fibers, owing to a reduction in the concentration of mobile myoplasmic buffers, so that in this preparation a pH gradient, if established within a sarcomere following action potential stimulation, could last 10 ms or longer after stimulation ceased.

Determination of acidity constants of curcumin in aqueous solution and apparent rate constant of its decomposition

NASA Astrophysics Data System (ADS)

Bernabé-Pineda, Margarita; Ramírez-Silva, María. Teresa; Romero-Romo, Mario; González-Vergara, Enrique; Rojas-Hernández, Alberto

2004-04-01

The stability of curcumin (H 3Cur) in aqueous media is improved when the systems in which it is present are at high pH values (higher than 11.7), fitting a model describable by a pseudo-zero order with a rate constant k' for the disappearance of the Cur 3- species of 1.39 (10 -9) M min -1. There were three acidity constants measured for the curcumin as follows: p KA3=10.51±0.01 corresponding to the equilibrium HCur 2-=Cur 3-+H +, a p KA2=9.88±0.02 corresponding to the equilibrium H 2Cur -=HCur -2+H +. These p KA values were attributed to the hydrogen of the phenol part of the curcumin, while the p KA1=8.38±0.04 corresponds to the equilibrium H 3Cur=H 2Cur -+H + and is attributed the acetylacetone type group. Formation of quinoid structures play an important role in the tautomeric forms of the curcumin in aqueous media, which makes the experimental values differ from the theoretically calculated ones, depending on the conditions adopted in the study.

Determination of association constants at moderately fast chemical exchange: complexation of camphor enantiomers by alpha-cyclodextrin.

PubMed

Bernatowicz, Piotr; Nowakowski, Michał; Dodziuk, Helena; Ejchart, Andrzej

2006-08-01

Association constants in weak molecular complexes can be determined by analysis of chemical shifts variations resulting from changes of guest to host concentration ratio. In the regime of very fast exchange, i.e., when exchange rate is several orders of magnitude larger than the Larmor angular frequency difference of the observed resonance in free and complexed molecule, the apparent position of averaged resonance is a population-weighted mean of resonances of particular forms involved in the equilibrium. The assumption of very fast exchange is often, however, tacitly admitted in literature even in cases where the process of interest is much slower than required. We show that such an unjustified simplification may, under certain circumstances, lead to significant underestimation of association constant and, in consequence, to non-negligible errors in Gibbs free energy under determination. We present a general method, based on iterative numerical NMR line shape analysis, which allows one for the compensation of chemical exchange effects, and delivers both the correct association constants and the exchange rates. The latter are not delivered by the other mentioned method. Practical application of our algorithm is illustrated by the case of camphor-alpha-cyclodextrin complexes.

Kinetics of enzymes with iso-mechanisms: analysis of product inhibition.

PubMed Central

Rebholz, K L; Northrop, D B

1993-01-01

Isomerizations of free enzyme can be detected in kinetic patterns of product inhibition when the isomerization is partially rate-limiting. The kinetic pattern is non-competitive, owing to binding of substrate and product to different forms of free enzyme. This adds an additional term to the rate equation, sometimes represented as KSP. Several kineticists have noted that, as the rate of isomerization becomes high in relation to catalytic turnover, the intercept effect will become small, KSP will approach infinity, and the pattern will look competitive. Britton [(1973) Biochem. J. 133, 255-261] asserted that KSP will also approach infinity when the rate of isomerization becomes low. This second assertion is incorrect and can be traced to the particular model and graphical representation used to examine KSP as a function of relative rate constants. The function portrayed as a parabola with two roots for KSP is, instead, a straight line with one root. The algebraic condition justifying the second root obtains in the limit of zero in the rate of reaction and thus is not experimentally relevant, and the appearance of competitive inhibition, based on KSP alone, is not valid. Using a more general model, new equations are derived and presented which provide direct calculations of the apparent rate constants for free enzyme isomerizations from product-inhibition data when the equilibrium of the isomerization is near 1, and useful limits for the rate constants when greater than or less than 1. PMID:7980736

Proton and metal ion binding to natural organic polyelectrolytes-II. Preliminary investigation with a peat and a humic acid

USGS Publications Warehouse

Marinsky, J.A.; Reddy, M.M.

1984-01-01

We summarize here experimental studies of proton and metal ion binding to a peat and a humic acid. Data analysis is based on a unified physico-chemical model for reaction of simple ions with polyelectrolytes employing a modified Henderson-Hasselbalch equation. Peat exhibited an apparent intrinsic acid dissociation constant of 10-4.05, and an apparent intrinsic metal ion binding constant of: 400 for cadmium ion; 600 for zinc ion; 4000 for copper ion; 20000 for lead ion. A humic acid was found to have an apparent intrinsic proton binding constant of 10-2.6. Copper ion binding to this humic acid sample occurred at two types of sites. The first site exhibited reaction characteristics which were independent of solution pH and required the interaction of two ligands on the humic acid matrix to simultaneously complex with each copper ion. The second complex species is assumed to be a simple monodentate copper ion-carboxylate species with a stability constant of 18. ?? 1984.

Larson-Miller Constant of Heat-Resistant Steel

NASA Astrophysics Data System (ADS)

Tamura, Manabu; Abe, Fujio; Shiba, Kiyoyuki; Sakasegawa, Hideo; Tanigawa, Hiroyasu

2013-06-01

Long-term rupture data for 79 types of heat-resistant steels including carbon steel, low-alloy steel, high-alloy steel, austenitic stainless steel, and superalloy were analyzed, and a constant for the Larson-Miller (LM) parameter was obtained in the current study for each material. The calculated LM constant, C, is approximately 20 for heat-resistant steels and alloys except for high-alloy martensitic steels with high creep resistance, for which C ≈ 30 . The apparent activation energy was also calculated, and the LM constant was found to be proportional to the apparent activation energy with a high correlation coefficient, which suggests that the LM constant is a material constant possessing intrinsic physical meaning. The contribution of the entropy change to the LM constant is not small, especially for several martensitic steels with large values of C. Deformation of such martensitic steels should accompany a large entropy change of 10 times the gas constant at least, besides the entropy change due to self-diffusion.

Catalytic Activity of μ-Carbido-Dimeric Iron(IV) Octapropylporphyrazinate in the 3,5,7,2',4'-Pentahydroxyflavone Oxidation Reaction with tert-Butyl Hydroperoxide

NASA Astrophysics Data System (ADS)

Tyurin, D. V.; Zaitseva, S. V.; Kudrik, E. V.

2018-05-01

It is found for the first time that μ-carbido-dimeric iron(IV) octapropylporphyrazinate displays catalytic activity in the oxidation reaction of natural flavonol morin with tert-butyl hydroperoxide, with the catalyst being stable under conditions of the reaction. The kinetics of this reaction are studied. It is shown the reaction proceeds via tentative formation of a complex between the catalyst and the oxidant, followed by O‒O bond homolytic cleavage. The kinetics of the reaction is described in the coordinates of the Michaelis-Menten equation. A linear dependence of the apparent reaction rate constant on the concentration of the catalyst is observed, testifying to its participation in the limiting reaction step. The equilibrium constants and rates of interaction are found. A mechanism is proposed for the reaction on the basis of the experimental data.

Pharmacokinetics of topically applied pilocarpine in the albino rabbit eye.

PubMed

Makoid, M C; Robinson, J R

1979-04-01

The temporal and spatial pattern of [3H]-pilocarpine nitrate distribution in the albino rabbit eye following topical administration was determined. A four-compartment caternary chain model describing this disposition corresponds to the precorneal area, the cornea, the aqueous humor, and the lens and vitreous. Simultaneous computer fitting of data from tissue corresponding to some compartments in the model supported the proposed model. Additional support was provided by the excellent correlation between predicted and observed values in multiple-dosing studies. Several important aspects of ocular drug disposition are evident from the model. The extensive parallel elimination at the absorption site gives rise to an apparent absorption rate constant that is one to two orders of magnitude larger than the true absorption rate constant. In addition, aqueous flow accounts for most of the drug removal. Thus, major effects on absorption and elimination, independent of the drug structure, suggest the possibility of similar pharmacokinetics for vastly different drugs.

Oxidation kinetics of guanine in DNA molecules adsorbed onto indium tin oxide electrodes.

PubMed

Armistead, P M; Thorp, H H

2001-02-01

Oligonucleotides containing the guanine nucleobase were adsorbed onto ITO electrodes from mixtures of DMF and acetate buffer. Chronocoulometry and chronoamperometry were performed on the modified electrodes in both phosphate buffer and buffer containing low concentrations of the inorganic complex Ru(bpy)3(2+) (bpy = 2,2' bipyridine), which catalyzes guanine oxidation. The charge and current evolution with and without the catalyst were compared to the charge and current evolution for electrodes that were treated with identical oligonucleotides that were substituted at every guanine with the electrochemically inert nucleobase hypoxanthine. Chronocoulometry over 2.5 s shows that roughly 2 electrons per guanine were transferred to the electrode in both the presence and absence of Ru(bpy)3(2+), although at a slower rate for the uncatalyzed process. Chronoamperograms measured over 250 ms can be fit to a double exponential decay, with the intensity of the fast component roughly 6-20 times greater than that of the slow component. First- and second-order rate constants for catalytic and direct guanine oxidation were determined from the fast component. The maximum catalytic enhancement for immobilized guanine was found to be i(cat)/i(d) = 4 at 25 microM Ru(bpy)3(2+). The second-order rate constant for the catalyzed reaction was 1.3 x 10(7) M(-1) s(-1), with an apparent dissociation constant of 8.8 microM. When compared to parallel studies in solution, a smaller value of the dissociation constant and a larger value of the second-order rate constant are observed, probably due to distortion of the immobilized DNA, an increase in the local negative charge due to the oxygen sites on the ITO surface, and redox cycling of the catalyst, which maintains the surface concentration of the active form.

A study of vapor-phase deposition of silicon nitride layers by ammonolysis of dichlorosilane at lowered pressure

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

Manzha, N. M., E-mail: magazine@miee.ru

2010-12-15

Deposition kinetics of silicon nitride layers at lowered reactor pressures of 10-130 Pa and temperatures in the range 973-1073 K has been studied. The equilibrium constant of the bimolecular reaction of dichlorosilane with ammonia has been calculated. The apparent activation energies calculated taking into account the experimental growth rate nearly coincide with the experimental data. Recommendations for improving the quality of silicon nitride layers are made.

Evaluation of photostability of solid-state nicardipine hydrochloride polymorphs by using Fourier-transformed reflection-absorption infrared spectroscopy - effect of grinding on the photostability of crystal form.

PubMed

Teraoka, Reiko; Otsuka, Makoto; Matsuda, Yoshihisa

2004-11-22

Photostability and physicochemical properties of nicardipine hydrochloride polymorphs (alpha- and beta-form) were studied by using Fourier-transformed reflection-absorption infrared spectroscopy (FT-IR-RAS) of the tablets, X-ray powder diffraction analysis, differential scanning calorimetry (DSC), and color difference measurement. It was clear from the results of FT-IR-RAS spectra after irradiation that nicardipine hydrochloride in the solid state decomposed to its pyridine derivative when exposed to light. The photostability of the ground samples of two forms was also measured in the same manner. The two crystalline forms of the drug changed to nearly amorphous form after 150 min grinding in a mixer mill. X-ray powder diffraction patterns of those ground samples showed almost halo patterns. The nicardipine hydrochloride content on the surface of the tablet was determined based on the absorbance at 1700 cm(-1) attributable to the C=O stretch vibration in FT-IR-RAS spectra before and after irradiation by fluorescent lamp (3500 lx). The photodegradation followed apparently the first-order kinetics for any sample. The apparent photodegradation rate constant of beta-form was greater than that of alpha-form. The ground samples decomposed rapidly under the same light irradiation as compared with the intact crystalline forms. The photodegradation rate constant decreased with increase of the heat of fusion. copyright 2004 Elsevier B.V.

On the expected relationships among apparent stress, static stress drop, effective shear fracture energy, and efficiency

USGS Publications Warehouse

Beeler, N.M.; Wong, T.-F.; Hickman, S.H.

2003-01-01

We consider expected relationships between apparent stress ??a and static stress drop ????s using a standard energy balance and find ??a = ????s (0.5 - ??), where ?? is stress overshoot. A simple implementation of this balance is to assume overshoot is constant; then apparent stress should vary linearly with stress drop, consistent with spectral theories (Brune, 1970) and dynamic crack models (Madariaga, 1976). Normalizing this expression by the static stress drop defines an efficiency ??sw = ??sa/????s as follows from Savage and Wood (1971). We use this measure of efficiency to analyze data from one of a number of observational studies that find apparent stress to increase with seismic moment, namely earthquakes recorded in the Cajon Pass borehole by Abercrombie (1995). Increases in apparent stress with event size could reflect an increase in seismic efficiency; however, ??sw for the Cajon earthquakes shows no such increase and is approximately constant over the entire moment range. Thus, apparent stress and stress drop co-vary, as expected from the energy balance at constant overshoot. The median value of ??sw for the Cajon earthquakes is four times lower than ??sw for laboratory events. Thus, these Cajon-recorded earthquakes have relatively low and approximately constant efficiency. As the energy balance requires ??sw = 0.5 - ??, overshoot can be estimated directly from the Savage-Wood efficiency; overshoot is positive for Cajon Pass earthquakes. Variations in apparent stress with seismic moment for these earthquakes result primarily from systematic variations in static stress drop with seismic moment and do not require a relative decrease in sliding resistance with increasing event size (dynamic weakening). Based on the comparison of field and lab determinations of the Savage-Wood efficiency, we suggest the criterion ??sw > 0.3 as a test for dynamic weakening in excess of that seen in the lab.

Chromatographic studies of drug interactions with alpha1-acid glycoprotein by ultrafast affinity extraction and peak profiling.

PubMed

Beeram, Sandya; Bi, Cong; Zheng, Xiwei; Hage, David S

2017-05-12

Interactions with serum proteins such as alpha 1 -acid glycoprotein (AGP) can have a significant effect on the behavior and pharmacokinetics of drugs. Ultrafast affinity extraction and peak profiling were used with AGP microcolumns to examine these processes for several model drugs (i.e., chlorpromazine, disopyramide, imipramine, lidocaine, propranolol and verapamil). The association equilibrium constants measured for these drugs with soluble AGP by ultrafast affinity extraction were in the general range of 10 4 -10 6 M -1 at pH 7.4 and 37°C and gave good agreement with literature values. Some of these values were dependent on the relative drug and protein concentrations that were present when using a single-site binding model; these results suggested a more complex mixed-mode interaction was actually present, which was also then used to analyze the data. The apparent dissociation rate constants that were obtained by ultrafast affinity extraction when using a single-site model varied from 0.14 to 7.0s -1 and were dependent on the relative drug and protein concentrations. Lower apparent dissociation rate constants were obtained by this approach as the relative amount of drug versus protein was decreased, with the results approaching those measured by peak profiling at low drug concentrations. This information should be useful in better understanding how these and other drugs interact with AGP in the circulation. In addition, the chromatographic approaches that were optimized and used in this report to examine these systems can be adapted for the analysis of other solute-protein interactions of biomedical interest. Copyright © 2017 Elsevier B.V. All rights reserved.

Choice with frequently changing food rates and food ratios.

PubMed

Baum, William M; Davison, Michael

2014-03-01

In studies of operant choice, when one schedule of a concurrent pair is varied while the other is held constant, the constancy of the constant schedule may exert discriminative control over performance. In our earlier experiments, schedules varied reciprocally across components within sessions, so that while food ratio varied food rate remained constant. In the present experiment, we held one variable-interval (VI) schedule constant while varying the concurrent VI schedule within sessions. We studied five conditions, each with a different constant left VI schedule. On the right key, seven different VI schedules were presented in seven different unsignaled components. We analyzed performances at several different time scales. At the longest time scale, across conditions, behavior ratios varied with food ratios as would be expected from the generalized matching law. At shorter time scales, effects due to holding the left VI constant became more and more apparent, the shorter the time scale. In choice relations across components, preference for the left key leveled off as the right key became leaner. Interfood choice approximated strict matching for the varied right key, whereas interfood choice hardly varied at all for the constant left key. At the shortest time scale, visit patterns differed for the left and right keys. Much evidence indicated the development of a fix-and-sample pattern. In sum, the procedural difference made a large difference to performance, except for choice at the longest time scale and the fix-and-sample pattern at the shortest time scale. © Society for the Experimental Analysis of Behavior.

Effect of Physicochemical Properties of Slag and Flux on the Removal Rate of Oxide Inclusion from Molten Steel

NASA Astrophysics Data System (ADS)

Park, Jun Seok; Park, Joo Hyun

2016-12-01

The slag-metal reaction experiments were carried out using a high-frequency induction furnace to confirm the effect of slag composition on the removal rate of inclusions in molten steel through the CaO-based slags. The apparent rate constant of oxygen removal ( k O) was obtained as a function of slag composition. It increased with increasing basicity, and the content of MgO and CaF2, whereas it decreased by increasing the content of Al2O3 in the slag. The removal rate of inclusions was strongly affected not only by the driving force of the chemical dissolution but also by the viscosity of the slags and fluxes.

Modification of kinetic parameters of glycogen phosphorylase from mantle tissue of Mytilus galloprovincialis by a phosphorylation mechanism.

PubMed

San Juan Serrano, F; Fernández González, M; Sánchez López, J L; García Martín, L O

1995-09-01

Initial rate and affinity studies on mantle Mytilus phosphorylase a were carried out in order to find possible differences in its kinetic properties with respect to phosphorylase b. Phosphorylase a was not stimulated for any AMP concentrations. Michaelis constants (Km) are 0.05 mg/ml glycogen, 1.15 mM inorganic phosphate and 1.50 mM glucose-1-phosphate. The Kms for the substrates, in the direction of glycogen breakdown, are enhanced by non-saturating concentrations of cosubstrate, without reducing the apparent maximum velocity. First order and hyperbolic kinetics and values of the allosteric constant smaller than 2 were observed. These results suggest a catalytic mechanism different to that shown for mantle Mytilus phosphorylase b.

Effects of packaging and heat transfer kinetics on drug-product stability during storage under uncontrolled temperature conditions.

PubMed

Nakamura, Toru; Yamaji, Takayuki; Takayama, Kozo

2013-05-01

To predict the stability of pharmaceutical preparations under uncontrolled temperature conditions accurately, a method to compute the average reaction rate constant taking into account the heat transfer from the atmosphere to the product was developed. The average reaction rate constants computed with taken into consideration heat transfer (κ(re) ) were then compared with those computed without taking heat transfer into consideration (κ(in) ). The apparent thermal diffusivity (κ(a) ) exerted some influence on the average reaction rate constant ratio (R, R = κ(re) /κ(in) ). In the regions where the κ(a) was large (above 1 h(-1) ) or very small, the value of R was close to 1. On the contrary, in the middle region (0.001-1 h(-1) ), the value of R was less than 1.The κ(a) of the central part of a large-size container and that of the central part of a paper case of 10 bottles of liquid medicine (100 mL) fell within this middle region. On the basis of the above-mentioned considerations, heat transfer may need to be taken into consideration to enable a more accurate prediction of the stability of actual pharmaceutical preparations under nonisothermal atmospheres. Copyright © 2013 Wiley Periodicals, Inc.

Cold Incineration of Chlorophenols in Aqueous Solution by Advanced Electrochemical Process Electro-Fenton. Effect of Number and Position of Chlorine Atoms on the Degradation Kinetics

NASA Astrophysics Data System (ADS)

Oturan, Nihal; Panizza, Marco; Oturan, Mehmet A.

2009-09-01

This study reports the kinetics of the degradation of several chlorophenols (CPs), such as monochlorophenols (2-chlorophenol and 4-chlorophenol), dichlorophenols (2,4-dichlorophenol and 2,6- dichlorophenol), trichlorophenols (2,3,5- trichlorophenol and 2,4,5-trichlorophenol), 2,3,5,6-tetrachlorophenol, and pentachlorophenol, by the electro-Fenton process using a carbon felt cathode and a Pt anode. The effect of number and the position of the chlorine atoms in the aromatic ring on the oxidative degradation rate was evaluated and discussed. The oxidation reaction of all the CPs with hydroxyl radicals evidenced a pseudo-first-order kinetics and the rate constant decreased with increasing the number of chlorine atoms. The absolute rate constant of second-order reaction kinetics between CPs and •OH was determined by the competition kinetics method in the range of (3.56-7.75) × 109 M-1 s-1 and follows the same sequence of the apparent rate constants. The mineralization of several CPs and of a mixture of all CPs under study was monitored by the total organic carbon (TOC) removal and the chlorine release during mineralization was followed by ion chromatography. Our results demonstrated that more chlorinated phenols are more difficult to mineralize; however for all the tested CPs, almost quantitative release of chloride ions was obtained after 6 h of treatment.

Reduction of Fe(III) colloids by Shewanella putrefaciens: A kinetic model

NASA Astrophysics Data System (ADS)

Bonneville, Steeve; Behrends, Thilo; van Cappellen, Philippe; Hyacinthe, Christelle; Röling, Wilfred F. M.

2006-12-01

A kinetic model for the microbial reduction of Fe(III) oxyhydroxide colloids in the presence of excess electron donor is presented. The model assumes a two-step mechanism: (1) attachment of Fe(III) colloids to the cell surface and (2) reduction of Fe(III) centers at the surface of attached colloids. The validity of the model is tested using Shewanella putrefaciens and nanohematite as model dissimilatory iron reducing bacteria and Fe(III) colloidal particles, respectively. Attachment of nanohematite to the bacteria is formally described by a Langmuir isotherm. Initial iron reduction rates are shown to correlate linearly with the relative coverage of the cell surface by nanohematite particles, hence supporting a direct electron transfer from membrane-bound reductases to mineral particles attached to the cells. Using internally consistent parameter values for the maximum attachment capacity of Fe(III) colloids to the cells, Mmax, the attachment constant, KP, and the first-order Fe(III) reduction rate constant, k, the model reproduces the initial reduction rates of a variety of fine-grained Fe(III) oxyhydroxides by S. putrefaciens. The model explains the observed dependency of the apparent Fe(III) half-saturation constant, Km∗, on the solid to cell ratio, and it predicts that initial iron reduction rates exhibit saturation with respect to both the cell density and the abundance of the Fe(III) oxyhydroxide substrate.

Phototransformation Rate Constants of PAHs Associated with Soot Particles

PubMed Central

Kim, Daekyun; Young, Thomas M.; Anastasio, Cort

2013-01-01

Photodegradation is a key process governing the residence time and fate of polycyclic aromatic hydrocarbons (PAHs) in particles, both in the atmosphere and after deposition. We have measured photodegradation rate constants of PAHs in bulk deposits of soot particles illuminated with simulated sunlight. The photodegradation rate constants at the surface (k0p), the effective diffusion coefficients (Deff), and the light penetration depths (z0.5) for PAHs on soot layers of variable thickness were determined by fitting experimental data with a model of coupled photolysis and diffusion. The overall disappearance rates of irradiated low molecular weight PAHs (with 2-3 rings) on soot particles were influenced by fast photodegradation and fast diffusion kinetics, while those of high molecular weight PAHs (with 4 or more rings) were apparently controlled by either the combination of slow photodegradation and slow diffusion kinetics or by very slow diffusion kinetics alone. The value of z0.5 is more sensitive to the soot layer thickness than the k0p value. As the thickness of the soot layer increases, the z0.5 values increase, but the k0p values are almost constant. The effective diffusion coefficients calculated from dark experiments are generally higher than those from the model fitting method for illumination experiments. Due to the correlation between k0p and z0.5 in thinner layers, Deff should be estimated by an independent method for better accuracy. Despite some limitations of the model used in this study, the fitted parameters were useful for describing empirical results of photodegradation of soot-associated PAHs. PMID:23247292

Kinetic studies on the reduction of iron ore nuggets by devolatilization of lean-grade coal

NASA Astrophysics Data System (ADS)

Biswas, Chanchal; Gupta, Prithviraj; De, Arnab; Chaudhuri, Mahua Ghosh; Dey, Rajib

2016-12-01

An isothermal kinetic study of a novel technique for reducing agglomerated iron ore by volatiles released by pyrolysis of lean-grade non-coking coal was carried out at temperature from 1050 to 1200°C for 10-120 min. The reduced samples were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and chemical analysis. A good degree of metallization and reduction was achieved. Gas diffusion through the solid was identified as the reaction-rate-controlling resistance; however, during the initial period, particularly at lower temperatures, resistance to interfacial chemical reaction was also significant, though not dominant. The apparent rate constant was observed to increase marginally with decreasing size of the particles constituting the nuggets. The apparent activation energy of reduction was estimated to be in the range from 49.640 to 51.220 kJ/mol and was not observed to be affected by the particle size. The sulfur and carbon contents in the reduced samples were also determined.

Random variability explains apparent global clustering of large earthquakes

USGS Publications Warehouse

Michael, A.J.

2011-01-01

The occurrence of 5 Mw ≥ 8.5 earthquakes since 2004 has created a debate over whether or not we are in a global cluster of large earthquakes, temporarily raising risks above long-term levels. I use three classes of statistical tests to determine if the record of M ≥ 7 earthquakes since 1900 can reject a null hypothesis of independent random events with a constant rate plus localized aftershock sequences. The data cannot reject this null hypothesis. Thus, the temporal distribution of large global earthquakes is well-described by a random process, plus localized aftershocks, and apparent clustering is due to random variability. Therefore the risk of future events has not increased, except within ongoing aftershock sequences, and should be estimated from the longest possible record of events.

Studies on long chain cis- and trans-acyl-CoA esters and Acyl-CoA dehydrogenase from rat heart mitochondria.

PubMed

Korsrud, G O; Conacher, H B; Jarvis, G A; Beare-Rogers, J L

1977-02-01

The beta-oxidation of long chain fatty acids was investigated in a preparation of rat heart mitochondria. The acyl-CoA esters of the cis and trans isomers of delta9-hexadecenoic, delta9-octadecenoic, delta11-eicosenoic, and delta13-docosenoic acids were prepared. Rates of the acyl-CoA reaction were determined with an extract from rat heart mitochondria. The apparent Michaelis constant (Km) and maximum velocity (Vmax) were calculated for each substrate. In general, apparent Vmax values decreased with increasing chain length of the monoenoic substrates. Reduced activity of acyl-CoA dehydrogenase with long chain acyl-CoA esters could have contributed to accumulation of lipids in hearts of rats fed diets containing long chain fatty acids.

Calcium-Induced Mitochondrial Permeability Transitions: Parameters of Ca2+ Ion Interactions with Mitochondria and Effects of Oxidative Agents.

PubMed

Golovach, Nina G; Cheshchevik, Vitali T; Lapshina, Elena A; Ilyich, Tatsiana V; Zavodnik, Ilya B

2017-04-01

We evaluated the parameters of Ca 2+ -induced mitochondrial permeability transition (MPT) pore formations, Ca 2+ binding constants, stoichiometry, energy of activation, and the effect of oxidative agents, tert-butyl hydroperoxide (tBHP), and hypochlorous acid (HOCl), on Ca 2+ -mediated process in rat liver mitochondria. From the Hill plot of the dependence of MPT rate on Ca 2+ concentration, we determined the order of interaction of Ca 2+ ions with the mitochondrial sites, n = 3, and the apparent K d = 60 ± 12 µM. We also found the apparent Michaelis-Menten constant, K m , for Ca 2+ interactions with mitochondria to be equal to 75 ± 20 µM, whereas that in the presence of 300 µM tBHP was 120 ± 20 µM. Using the Arrhenius plots of the temperature dependences of apparent mitochondrial swelling rate at various Ca 2+ concentrations, we calculated the activation energy of the MPT process. ΔE a was 130 ± 20 kJ/mol at temperatures below the break point of the Arrhenius plot (30-34 °C) and 50 ± 9 kJ/mol at higher temperatures. Ca 2+ ions induced rapid mitochondrial NADH depletion and membrane depolarization. Prevention of the pore formation by cyclosporin A inhibited Ca 2+ -dependent mitochondrial depolarization and Mg 2+ ions attenuated the potential dissipation. tBHP (10-150 µM) dose-dependently enhanced the rate of MPT opening, whereas the effect of HOCl on MPT depended on the ratio of HOCl/Ca 2+ . The apparent K m of tBHP interaction with mitochondria in the swelling reaction was found to be K m = 11 ± 3 µM. The present study provides evidence that three calcium ions interact with mitochondrial site with high affinity during MPT. Ca 2+ -induced MPT pore formations due to mitochondrial membrane protein denaturation resulted in membrane potential dissipation. Oxidants with different mechanisms, tBHP and HOCl, reduced mitochondrial membrane potential and oxidized mitochondrial NADH in EDTA-free medium and had an effect on Ca 2+ -induced MPT onset.

The kinetics of competitive antagonists on guinea-pig ileum.

PubMed Central

Roberts, F; Stephenson, R P

1976-01-01

1 The kinetics of action of some competitive muscarinic and histamine antagonists were examined on guinea-pig isolated ileum and their behaviour compared with the predictions of the interaction-limited model described by Paton (1961). 2 The kinetics of antagonism were not consistent with the predictions of this model: (1) The apparent dissociation rate constant calculated from the decrease in occupancy on washout was not independent of the concentration of antagonist. (2) The dissociation rate constant of a 'slow' antagonist calculated from the change in occupancy when a 'fast' antagonist was superimposed varied with the concentration of fast antagonist. (3) If the concentration of slow antagonist was increased when the fast antagonist was superimposed so that the equilibrium occupancy of the 'slow' was the same as before, a transitional phase was observed. 3 The kinetics of antagonism were observed in longitudinal muscle strips and intact pieces of ileum, bathed in Tyrode or Krebs solution, and with isometric and isotonic recording. No evidence was found that the discrepancies between the interaction-limited model and the observed kinetics could be accounted for by the experimental method used. 4 It is therefore concluded that either access is rate-limiting in these circumstances or, if interaction is rate-limiting, some alternative interaction-limited model is required to describe the kinetics of antagonism. In either case it would seem unwise at this time to calculate antagonist-receptor rate constants from the observed kinetics of antagonism. PMID:974378

Ocean chemistry, ocean warming, and emerging hypoxia: Commentary

NASA Astrophysics Data System (ADS)

Brewer, Peter G.; Peltzer, Edward T.

2016-05-01

For 50 years, ocean scientists have represented deep sea biogeochemical rates as a temperature independent function of depth with form R = R0e-αz where z is depth in km. We show this resembles, but is not an identity for, a form of the classical Arrhenius equation K = Ae-Ea/RT where T is temperature in Kelvins, R is the gas constant (8.314 JK-1mol-1), and A is a preexponential factor. For a deep Sargasso Sea data set, we find oxygen consumption rates are accurately represented by an Arrhenius process with apparent activation energy of 86.5 kJ mol-1, and Q10 = 3.63.

Steady-state studies of the reactions of H2O-CO and CO2-H2 mixtures with liquid iron

NASA Astrophysics Data System (ADS)

Sasaki, Y.; Belton, G. R.

1998-08-01

Studies have been made of the steady-stata composition of liquid iron exposed to high flow rates of H2O-CO mixtures at 1550 °C to 1700 °C and CO2-H2 mixtures at 1600 °C. Values of the steady-state activity of oxygen have been established by measurement of either the carbon concentration or the silicon concentration when the iron was held in a silica crucible. Additions of sulfur or selenium to the iron have been found to result in steady-state oxygen activities, which differ significantly from those expected from water-gas equilibrium. The results are interpreted to show that the ratio of the apparent first-order rate constants for the reactions of H2O and CO2 with liquid iron is about 3 at 1600 °C. It is shown that the dependencies of the rate constants on the activities of sulfur, oxygen, and selenium must, even if complex, be similar for the H2O and CO2 reactions with liquid iron, to a good approximation.

The Thermochemical and Kinetic Properties of Ascorbate are Tuned by its Local Environment: Solution Chemistry and Biochemical Implications

PubMed Central

Warren, Jeffrey J.; Mayer, James M.

2010-01-01

Ascorbate (Vitamin C) is a ubiquitous biological cofactor. While its aqueous solution chemistry has long been studied, many in vivo reactions of ascorbate occur in enzyme active sites or at membrane interfaces, which have varying local environments. This report shows that the rate and driving force of oxidations of two ascorbate derivatives by the TEMPO radical (2,2′-6,6′-tetramethylpiperidine-1-oxyl) in acetonitrile are very sensitive to the presence of various additives. These reactions proceed by the transfer of a proton and an electron (a hydrogen atom), as is typical of biological ascorbate reactions. The measured rate and equilibrium constants vary substantially with added water or other polar solutes in acetonitrile solutions, indicating large shifts in the reducing power of ascorbate. The correlation of rate and equilibrium constants indicates that this effect has a thermochemical origin rather than being a purely kinetic effect. This contrasts with previous examples of solvent effects on hydrogen atom transfer reactions. Potential biological implications of this apparently unique effect are discussed. PMID:20476757

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

Effects of para-substituents of styrene derivatives on their chemical reactivity on platinum nanoparticle surfaces

NASA Astrophysics Data System (ADS)

Hu, Peiguang; Chen, Limei; Deming, Christopher P.; Lu, Jia-En; Bonny, Lewis W.; Chen, Shaowei

2016-06-01

Stable platinum nanoparticles were successfully prepared by the self-assembly of para-substituted styrene derivatives onto the platinum surfaces as a result of platinum-catalyzed dehydrogenation and transformation of the vinyl groups to the acetylene ones, forming platinum-vinylidene/-acetylide interfacial bonds. Transmission electron microscopic measurements showed that the nanoparticles were well dispersed without apparent aggregation, suggesting sufficient protection of the nanoparticles by the organic capping ligands, and the average core diameter was estimated to be 2.0 +/- 0.3 nm, 1.3 +/- 0.2 nm, and 1.1 +/- 0.2 nm for the nanoparticles capped with 4-tert-butylstyrene, 4-methoxystyrene, and 4-(trifluoromethyl)styrene, respectively, as a result of the decreasing rate of dehydrogenation with the increasing Taft (polar) constant of the para-substituents. Importantly, the resulting nanoparticles exhibited unique photoluminescence, where an increase of the Hammett constant of the para-substituents corresponded to a blue-shift of the photoluminescence emission, suggesting an enlargement of the HOMO-LUMO band gap of the nanoparticle-bound acetylene moieties. Furthermore, the resulting nanoparticles exhibited apparent electrocatalytic activity towards oxygen reduction in acidic media, with the best performance among the series of samples observed with the 4-tert-butylstyrene-capped nanoparticles due to an optimal combination of the nanoparticle core size and ligand effects on the bonding interactions between platinum and oxygen species.Stable platinum nanoparticles were successfully prepared by the self-assembly of para-substituted styrene derivatives onto the platinum surfaces as a result of platinum-catalyzed dehydrogenation and transformation of the vinyl groups to the acetylene ones, forming platinum-vinylidene/-acetylide interfacial bonds. Transmission electron microscopic measurements showed that the nanoparticles were well dispersed without apparent aggregation, suggesting sufficient protection of the nanoparticles by the organic capping ligands, and the average core diameter was estimated to be 2.0 +/- 0.3 nm, 1.3 +/- 0.2 nm, and 1.1 +/- 0.2 nm for the nanoparticles capped with 4-tert-butylstyrene, 4-methoxystyrene, and 4-(trifluoromethyl)styrene, respectively, as a result of the decreasing rate of dehydrogenation with the increasing Taft (polar) constant of the para-substituents. Importantly, the resulting nanoparticles exhibited unique photoluminescence, where an increase of the Hammett constant of the para-substituents corresponded to a blue-shift of the photoluminescence emission, suggesting an enlargement of the HOMO-LUMO band gap of the nanoparticle-bound acetylene moieties. Furthermore, the resulting nanoparticles exhibited apparent electrocatalytic activity towards oxygen reduction in acidic media, with the best performance among the series of samples observed with the 4-tert-butylstyrene-capped nanoparticles due to an optimal combination of the nanoparticle core size and ligand effects on the bonding interactions between platinum and oxygen species. Electronic supplementary information (ESI) available: TGA curves and additional voltammograms. See DOI: 10.1039/c6nr02296k

Synthesis of molecular imprinted polymer modified TiO{sub 2} nanotube array electrode and their photoelectrocatalytic activity

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

Lu Na; Chen Shuo; Wang Hongtao

2008-10-15

A tetracycline hydrochloride (TC) molecularly imprinted polymer (MIP) modified TiO{sub 2} nanotube array electrode was prepared via surface molecular imprinting. Its surface was structured with surface voids and the nanotubes were open at top end with an average diameter of approximately 50 nm. The MIP-modified TiO{sub 2} nanotube array with anatase phase was identified by XRD and a distinguishable red shift in the absorption spectrum was observed. The MIP-modified electrode also exhibited a high adsorption capacity for TC due to its high surface area providing imprinted sites. Photocurrent was generated on the MIP-modified photoanode using the simulated solar spectrum andmore » increased with the increase of positive bias potential. Under simulated solar light irradiation, the MIP-modified TiO{sub 2} nanotube array electrode exhibited enhanced photoelectrocatalytic (PEC) activity with the apparent first-order rate constant being 1.2-fold of that with TiO{sub 2} nanotube array electrode. The effect of the thickness of the MIP layer on the PEC activity was also evaluated. - Graphical abstract: A tetracycline hydrochloride molecularly imprinted polymer modified TiO{sub 2} nanotube array electrode was prepared via surface molecular imprinting. It showed improved response to simulated solar light and higher adsorption capability for tetracycline hydrochloride, thereby exhibiting increased PEC activity under simulated solar light irradiation. The apparent first-order rate constant was 1.2-fold of that on TiO{sub 2} nanotube array electrode.« less

Kinetics of reduction of plutonium(VI) and neptunium(VI) by sulfide in neutral and alkaline solutions

USGS Publications Warehouse

Nash, K.L.; Cleveland, J.M.; Sullivan, J.C.; Woods, M.

1986-01-01

The rate of reduction of plutonium(VI) and neptunium(VI) by bisulfide ion in neutral and mildly alkaline solutions has been investigated by the stopped-flow technique. The reduction of both of these ions to the pentavalent oxidation state appears to occur in an intramolecular reaction involving an unusual actinide(VI)-hydroxide-bisulfide complex. For plutonium the rate of reduction is 27.4 (??4.1) s-1 at 25??C with ??H* = +33.2 (??1.0) kJ/mol and ??S* = -106 (??4) J/(mol K). The apparent stability constant for the transient complex is 4.66 (??0.94) ?? 103 M-1 at 25??C with associated thermodynamic parameters of ??Hc = +27.7 (??0.4) kJ/mol and ??Sc = +163 (??2) J/(mol K). The corresponding rate and stability constants are determined for the neptunium system at 25??C (k3 = 139 (??30) s-1, Kc. = 1.31 (??0.32) ?? 103 M-1), but equivalent parameters cannot be determined at reduced temperatures. The reaction rate is decreased by bicarbonate ion. At pH > 10.5, a second reaction mechanism, also involving a sulfide complex, is indicated. ?? 1986 American Chemical Society.

The Investigation of Electrochemistry Behaviors of Tyrosinase Based on Directly-Electrodeposited Grapheneon Choline-Gold Nanoparticles.

PubMed

He, Yaping; Yang, Xiaohui; Han, Quan; Zheng, Jianbin

2017-06-23

A novel catechol (CA) biosensor was developed by embedding tyrosinase (Tyr) onto in situ electrochemical reduction graphene (EGR) on choline-functionalized gold nanoparticle (AuNPs-Ch) film. The results of UV-Vis spectra indicated that Tyr retained its original structure in the film, and an electrochemical investigation of the biosensor showed a pair of well-defined, quasi-reversible redox peaks with E pa = -0.0744 V and E pc = -0.114 V (vs. SCE) in 0.1 M, pH 7.0 sodium phosphate-buffered saline at a scan rate of 100 mV/s. The transfer rate constant k s is 0.66 s -1 . The Tyr-EGR/AuNPs-Ch showed a good electrochemical catalytic response for the reduction of CA, with the linear range from 0.2 to 270 μM and a detection limit of 0.1 μM (S/N = 3). The apparent Michaelis-Menten constant was estimated to be 109 μM.

In vitro activity of minimised hammerhead ribozymes.

PubMed Central

Hendry, P; McCall, M J; Santiago, F S; Jennings, P A

1995-01-01

A number of minimised hammerhead ribozymes (minizymes) which lack stem II have been kinetically characterised. These minizymes display optimal cleavage activity at temperatures around 37 degrees C. The cleavage reactions of the minizymes are first order in hydroxide ion concentration up to around pH 9.3 above which the cleavage rate constants decline rapidly. The reactions show a biphasic dependence on magnesium-ion concentration; one of the interactions has an apparent dissociation constant of around 20 mM while the other appears to be very weak, showing no sign of saturation at 200 mM MgCl2. The minizymes are significantly less active than comparable, full-size ribozymes when cleaving short substrates. However, at a particular site in a transcribed TAT gene from HIV-1, minizymes are more effective than ribozymes. PMID:7479037

A novel hydrogen peroxide biosensor based on hemoglobin-collagen-CNTs composite nanofibers.

PubMed

Li, J; Mei, H; Zheng, W; Pan, P; Sun, X J; Li, F; Guo, F; Zhou, H M; Ma, J Y; Xu, X X; Zheng, Y F

2014-06-01

In this paper, carbon nanotubes (CNTs) were successfully incorporated in the composite composed of hemoglobin (Hb) and collagen using co-electrospinning technology. The formed Hb-collagen-CNTs composite nanofibers possessed distinct advantage of three-dimensional porous structure, biocompatibility and excellent stability. The Hb immobilized in the electrospun nanofibers retained its natural structure and the heterogeneous electron transfer rate constant (ks) of the direct electron transfer between Hb and electrodes was 5.3s(-1). In addition, the electrospun Hb-collagen-CNTs nanofibers modified electrodes showed good electrocatalytic properties toward H2O2 with a detection limit of 0.91μM (signal-to-noise ratio of 3) and the apparent Michaelis-Menten constant (Km(app)) of 32.6μM. Copyright © 2014 Elsevier B.V. All rights reserved.

Purification and Thermal Dependence of Glutathione Reductase from Two Forage Legume Species 1

PubMed Central

Kidambi, Saranga P.; Mahan, James R.; Matches, Arthur G.

1990-01-01

Alfalfa (Medicago sativa L.) and sainfoin (Onobrychis viciifolia Scop.) are forage legumes that differ in their responses to high and low temperature stresses. Thermal limitations on the function of glutathione reductase (EC 1.6.4.2) could adversely affect the ability of the plant to cope with adverse temperatures. Our objectives were to (a) purify glutathione reductase from `Cimarron' alfalfa and `PI 212241' sainfoin and (b) investigate the intraspecies variation in the thermal dependency of glutathione reductase from each of three cultivars of alfalfa and two cultivars and an introduction of sainfoin. Glutathione reductase was purified 1222-and 1948-fold to a specific activity of 281 and 273 units per milligram of protein, from one species each of alfalfa and sainfoin, respectively. The relative molecular mass of the protein was approximately 140 kilodaltons with subunits of 57 and 37 kilodaltons under denaturing conditions. The activation energies were approximately 50 kilojoules per mole for both species. Over a 5 to 45°C temperature gradient, large variation among species and genotypes within species was found for: (a) the minimum apparent Michaelis constant (0.6-2.1 micromoles of NADPH), (b) the temperature at which the minimum apparent Michaelis constant was observed (10-25°C), and (c) the thermal kinetic windows (6-19°C width). Future studies will focus on relating the thermal dependence of the Michaelis constant of the glutathione reductases and plant growth rates and forage quality of these species throughout the growing season. PMID:16667283

Spectral and kinetic studies of the oxidation of monosubstituted phenols and anilines by recombinant Synechocystis catalase-peroxidase compound I.

PubMed

Regelsberger, G; Jakopitsch, C; Engleder, M; Rüker, F; Peschek, G A; Obinger, C

1999-08-10

A high-level expression in Escherichia coli of a fully active recombinant form of a catalase-peroxidase (KatG) from the cyanobacterium Synechocystis PCC 6803 is reported. Since both physical and kinetic characterization revealed its identity with the wild-type protein, the large quantities of recombinant KatG allowed the first examination of second-order rate constants for the oxidation of a series of aromatic donor molecules (monosubstituted phenols and anilines) by a bifunctional catalase-peroxidase compound I using the sequential-mixing stopped-flow technique. Because of the overwhelming catalase activity, peroxoacetic acid has been used for compound I formation. A >/=50-fold excess of peroxoacetic acid is required to obtain a spectrum of relatively pure and stable compound I which is characterized by about 40% hypochromicity, a Soret maximum at 406 nm, and isosbestic points between the native enzyme and compound I at 357 and 430 nm. The apparent second-order rate constant for formation of compound I from ferric enzyme and peroxoacetic acid is (8.74 +/- 0.26) x 10(3) M(-)(1) s(-)(1) at pH 7. 0. Reduction of compound I by aromatic donor molecules is dependent upon the substituent effect on the benzene ring. The apparent second-order rate constants varied from (3.6 +/- 0.1) x 10(6) M(-)(1) s(-)(1) for p-hydroxyaniline to (5.0 +/- 0.1) x 10(2) M(-)(1) s(-)(1) for p-hydroxybenzenesulfonic acid. They are shown to correlate with the substituent constants in the Hammett equation, which suggests that in bifunctional catalase-peroxidases the aromatic donor molecule donates an electron to compound I and loses a proton simultaneously. The value of rho, the susceptibility factor in the Hammett equation, is -3.4 +/- 0.4 for the phenols and -5.1 +/- 0.8 for the anilines. The pH dependence of compound I reduction by aniline exhibits a relatively sharp maximum at pH 5. The redox intermediate formed upon reduction of compound I has spectral features which indicate that the single oxidizing equivalent in KatG compound II is contained on an amino acid which is not electronically coupled to the heme.

Some Fundamental Experiments on Apparent Dissolution Rate of Gas Phase in the Groundwater Recovery Processes of the Geological Disposal System - 12146

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

Yoshii, Taiki; Niibori, Yuichi; Mimura, Hitoshi

The apparent dissolution rates of gas phase in the co-presence of solid phase were examined by in-room experiments in this study. The apparent dissolution rate of gas phase q (mol/m{sup 3}.s) was generally defined by q=aK{sub L}(γP{sub g}-c), where a (1/m) is specific surface area of the interface between gas and liquid phases, K{sub L} (m/s) is overall mass transfer coefficient, γ (mol/(Pa.m{sup 3})) is reciprocal number of Henry constant, P{sub g} (Pa) is partial pressure of gas phase, and c (mol/m{sup 3}) is the concentration of gas component in liquid phase. As a model gas, CO{sub 2} gas wasmore » used. For evaluating the values of K{sub L}, this study monitored pH or the migration rate of the interface between water/gas phases, using some experiments such as the packed beds and the micro channel consisting of granite chip and rubber sheet including a slit. In the results, the values of K{sub L} were distributed in the range from 5.0x10{sup -6} m/s to 5.0x10{sup -7} m/s. These values were small, in comparison with that (7.8x10{sup -4} m/s) obtained from the bubbling test where gas phase was continually injected into deionized water without solid phase. This means that the solid phase limits the local mixing of water phase near gas-liquid interfaces. (authors)« less

Stress corrosion crack initiation of Zircaloy-4 cladding tubes in an iodine vapor environment during creep, relaxation, and constant strain rate tests

NASA Astrophysics Data System (ADS)

Jezequel, T.; Auzoux, Q.; Le Boulch, D.; Bono, M.; Andrieu, E.; Blanc, C.; Chabretou, V.; Mozzani, N.; Rautenberg, M.

2018-02-01

During accidental power transient conditions with Pellet Cladding Interaction (PCI), the synergistic effect of the stress and strain imposed on the cladding by thermal expansion of the fuel, and corrosion by iodine released as a fission product, may lead to cladding failure by Stress Corrosion Cracking (SCC). In this study, internal pressure tests were conducted on unirradiated cold-worked stress-relieved Zircaloy-4 cladding tubes in an iodine vapor environment. The goal was to investigate the influence of loading type (constant pressure tests, constant circumferential strain rate tests, or constant circumferential strain tests) and test temperature (320, 350, or 380 °C) on iodine-induced stress corrosion cracking (I-SCC). The experimental results obtained with different loading types were consistent with each other. The apparent threshold hoop stress for I-SCC was found to be independent of the test temperature. SEM micrographs of the tested samples showed many pits distributed over the inner surface, which tended to coalesce into large pits in which a microcrack could initiate. A model for the time-to-failure of a cladding tube was developed using finite element simulations of the viscoplastic mechanical behavior of the material and a modified Kachanov's damage growth model. The times-to-failure predicted by this model are consistent with the experimental data.

Phototransformation rate constants of PAHs associated with soot particles.

PubMed

Kim, Daekyun; Young, Thomas M; Anastasio, Cort

2013-01-15

Photodegradation is a key process governing the residence time and fate of polycyclic aromatic hydrocarbons (PAHs) in particles, both in the atmosphere and after deposition. We have measured photodegradation rate constants of PAHs in bulk deposits of soot particles illuminated with simulated sunlight. The photodegradation rate constants at the surface (k(p)(0)), the effective diffusion coefficients (D(eff)), and the light penetration depths (z(0.5)) for PAHs on soot layers of variable thickness were determined by fitting experimental data with a model of coupled photolysis and diffusion. The overall disappearance rates of irradiated low molecular weight PAHs (with 2-3 rings) on soot particles were influenced by fast photodegradation and fast diffusion kinetics, while those of high molecular weight PAHs (with 4 or more rings) were apparently controlled by either the combination of slow photodegradation and slow diffusion kinetics or by very slow diffusion kinetics alone. The value of z(0.5) is more sensitive to the soot layer thickness than the k(p)(0) value. As the thickness of the soot layer increases, the z(0.5) values increase, but the k(p)(0) values are almost constant. The effective diffusion coefficients calculated from dark experiments are generally higher than those from the model fitting method for illumination experiments. Due to the correlation between k(p)(0) and z(0.5) in thinner layers, D(eff) should be estimated by an independent method for better accuracy. Despite some limitations of the model used in this study, the fitted parameters were useful for describing empirical results of photodegradation of soot-associated PAHs. Copyright © 2012 Elsevier B.V. All rights reserved.

Dynamics of Soil Water Evaporation during Soil Drying in the Presence of a Shallow Water Table: Laboratory Experiment and Numerical Analysis

NASA Astrophysics Data System (ADS)

Han, J.; Lin, J.; Liu, P.; Li, W.

2017-12-01

Evaporation from a porous medium plays a key role in hydrological, agricultural, environmental, and engineering applications. Laboratory and numerical experiments were conducted to investigate the evolution of soil water evaporation during a continuous drying event. Simulated soil water contents and temperatures by the calibrated model well reproduced measured values at different depths. Results show that the evaporative drying process could be divided into three stages, beginning with a relatively high evaporation rate during stage 1, followed by a lower rate during transient stage and stage 2, and finally maintaining a very low and constant rate during stage 3. The condensation zone was located immediately below the evaporation zone in the profile. Both peaks of evaporation and condensation rate increased rapidly during stage 1 and transition stage, decreased during stage 2, and maintained constant during stage 3. The width of evaporation zone kept a continuous increase during stages 1 and 2 and maintained a nearly constant value of 0.68 cm during stage 3. When the evaporation zone totally moved into the subsurface, a dry surface layer (DSL) formed above the evaporation zone at the end of stage 2. The width of DSL also presented a continuous increase during stage 2 and kept a constant value of 0.71 cm during stage 3. Although the magnitude of condensation zone was much smaller than that for the evaporation zone, the importance of the contribution of condensation zone to soil water dynamics should not be underestimated. Results from our experiment and numerical simulation show that this condensation process resulted in an unexpected and apparent water content increase in the middle of vadose zone profile.

Characterization of a Naphthalene Dioxygenase Endowed with an Exceptionally Broad Substrate Specificity Toward Polycyclic Aromatic Hydrocarbons

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

Jouanneau,Y.; Meyer, C.; Jakoncic, J.

In Sphingomonas CHY-1, a single ring-hydroxylating dioxygenase is responsible for the initial attack of a range of polycyclic aromatic hydrocarbons (PAHs) composed of up to five rings. The components of this enzyme were separately purified and characterized. The oxygenase component (ht-PhnI) was shown to contain one Rieske-type [2Fe-2S] cluster and one mononuclear Fe center per {alpha} subunit, based on EPR measurements and iron assay. Steady-state kinetic measurements revealed that the enzyme had a relatively low apparent Michaelis constant for naphthalene (K{sub m} = 0.92 {+-} 0.15 {mu}M) and an apparent specificity constant of 2.0 {+-} 0.3 M{sup -1} s{sup -1}.more » Naphthalene was converted to the corresponding 1,2-dihydrodiol with stoichiometric oxidation of NADH. On the other hand, the oxidation of eight other PAHs occurred at slower rates and with coupling efficiencies that decreased with the enzyme reaction rate. Uncoupling was associated with hydrogen peroxide formation, which is potentially deleterious to cells and might inhibit PAH degradation. In single turnover reactions, ht-PhnI alone catalyzed PAH hydroxylation at a faster rate in the presence of organic solvent, suggesting that the transfer of substrate to the active site is a limiting factor. The four-ring PAHs chrysene and benz[a]anthracene were subjected to a double ring-dihydroxylation, giving rise to the formation of a significant proportion of bis-cis-dihydrodiols. In addition, the dihydroxylation of benz[a]anthracene yielded three dihydrodiols, the enzyme showing a preference for carbons in positions 1,2 and 10,11. This is the first characterization of a dioxygenase able to dihydroxylate PAHs made up of four and five rings.« less

The Reaction Kinetics of 3-Hydroxybenzoate 6-Hydroxylase from Rhodococcus jostii RHA1 Provide an Understanding of the para-Hydroxylation Enzyme Catalytic Cycle*

PubMed Central

Sucharitakul, Jeerus; Tongsook, Chanakan; Pakotiprapha, Danaya; van Berkel, Willem J. H.; Chaiyen, Pimchai

2013-01-01

3-Hydroxybenzoate 6-hydroxylase (3HB6H) from Rhodococcus jostii RHA1 is an NADH-specific flavoprotein monooxygenase that catalyzes the para-hydroxylation of 3-hydroxybenzoate (3HB) to form 2,5-dihydroxybenzoate (2,5-DHB). Based on results from stopped-flow spectrophotometry, the reduced enzyme-3HB complex reacts with oxygen to form a C4a-peroxy flavin with a rate constant of 1.13 ± 0.01 × 106 m−1 s−1 (pH 8.0, 4 °C). This intermediate is subsequently protonated to form a C4a-hydroperoxyflavin with a rate constant of 96 ± 3 s−1. This step shows a solvent kinetic isotope effect of 1.7. Based on rapid-quench measurements, the hydroxylation occurs with a rate constant of 36 ± 2 s−1. 3HB6H does not exhibit substrate inhibition on the flavin oxidation step, a common characteristic found in most ortho-hydroxylation enzymes. The apparent kcat at saturating concentrations of 3HB, NADH, and oxygen is 6.49 ± 0.02 s−1. Pre-steady state and steady-state kinetic data were used to construct the catalytic cycle of the reaction. The data indicate that the steps of product release (11.7 s−1) and hydroxylation (36 ± 2 s−1) partially control the overall turnover. PMID:24129570

Effect of positive pulse charge waveforms on cycle life of nickel-zinc cells

NASA Technical Reports Server (NTRS)

Smithrick, J. J.

1980-01-01

Five amp-hour nickel-zinc cells were life cycled to evaluate four different charge methods. Three of the four waveforms investigated were 120 Hz full wave rectified sinusoidal (FWRS), 120 Hz silicon controlled rectified (SCR), and 1 kHz square wave (SW). The fourth, a constant current method, was used as a baseline of comparison. Three sealed Ni-Zn cells connected in series were cycled. Each series string was charged at an average c/20 rate, and discharged at a c/2.5 rate to a 75% rated depth. Results indicate that the relatively inexpensive 120 Hz FWRS charger appears feasible for charging 5 amp-hour nickel-zinc cells with no significant loss in average cycle life when compared to constant current charging. The 1-kHz SW charger could also be used with no significant loss in average cycle life, and suggests the possibility of utilizing the existing electric vehicle chopper controller circuitry for an on-board charger. There was an apparent difference using the 120 Hz SCR charger compared to the others, however, this difference could be due to an inadvertent severe overcharge, which occurred prior to cell failure. The remaining two positive pulse charging waveforms, FWRS and 1 kHz, did not improve the cycle life of 5 amp-hour nickel-zinc cells over that of constant current charging.

Apparent-contact-angle model at partial wetting and evaporation: impact of surface forces.

PubMed

Janeček, V; Nikolayev, V S

2013-01-01

This theoretical and numerical study deals with evaporation of a fluid wedge in contact with its pure vapor. The model describes a regime where the continuous wetting film is absent and the actual line of the triple gas-liquid-solid contact appears. A constant temperature higher than the saturation temperature is imposed at the solid substrate. The fluid flow is solved in the lubrication approximation. The introduction of the surface forces in the case of the partial wetting is discussed. The apparent contact angle (the gas-liquid interface slope far from the contact line) is studied numerically as a function of the substrate superheating, contact line velocity, and parameters related to the solid-fluid interaction (Young and microscopic contact angles, Hamaker constant, etc.). The dependence of the apparent contact angle on the substrate temperature is in agreement with existing approaches. For water, the apparent contact angle may be 20° larger than the Young contact angle for 1 K superheating. The effect of the surface forces on the apparent contact angle is found to be weak.

Apparent-contact-angle model at partial wetting and evaporation: Impact of surface forces

NASA Astrophysics Data System (ADS)

Janeček, V.; Nikolayev, V. S.

2013-01-01

This theoretical and numerical study deals with evaporation of a fluid wedge in contact with its pure vapor. The model describes a regime where the continuous wetting film is absent and the actual line of the triple gas-liquid-solid contact appears. A constant temperature higher than the saturation temperature is imposed at the solid substrate. The fluid flow is solved in the lubrication approximation. The introduction of the surface forces in the case of the partial wetting is discussed. The apparent contact angle (the gas-liquid interface slope far from the contact line) is studied numerically as a function of the substrate superheating, contact line velocity, and parameters related to the solid-fluid interaction (Young and microscopic contact angles, Hamaker constant, etc.). The dependence of the apparent contact angle on the substrate temperature is in agreement with existing approaches. For water, the apparent contact angle may be 20∘ larger than the Young contact angle for 1 K superheating. The effect of the surface forces on the apparent contact angle is found to be weak.

Total individual ion activity coefficients of calcium and carbonate in seawater at 25°C and 35%. salinity, and implications to the agreement between apparent and thermodynamic constants of calcite and aragonite

USGS Publications Warehouse

Plummer, Niel; Sundquist, Eric T.

1982-01-01

We have calculated the total individual ion activity coefficients of carbonate and calcium,  and , in seawater. Using the ratios of stoichiometric and thermodynamic constants of carbonic acid dissociation and total mean activity coefficient data measured in seawater, we have obtained values which differ significantly from those widely accepted in the literature. In seawater at 25°C and 35%. salinity the (molal) values of  and  are 0.038 ± 0.002 and 0.173 ± 0.010, respectively. These values of  and  are independent of liquid junction errors and internally consistent with the value . By defining  and  on a common scale (), the product  is independent of the assigned value of  and may be determined directly from thermodynamic measurements in seawater. Using the value  and new thermodynamic equilibrium constants for calcite and aragonite, we show that the apparent constants of calcite and aragonite are consistent with the thermodynamic equilibrium constants at 25°C and 35%. salinity. The demonstrated consistency between thermodynamic and apparent constants of calcite and aragonite does not support a hypothesis of stable Mg-calcite coatings on calcite or aragonite surfaces in seawater, and suggests that the calcite critical carbonate ion curve of Broecker and Takahashi (1978,Deep-Sea Research25, 65–95) defines the calcite equilibrium boundary in the oceans, within the uncertainty of the data.

Temperature dependence of internal friction in enzyme reactions.

PubMed

Rauscher, Anna Á; Simon, Zoltán; Szöllosi, Gergely J; Gráf, László; Derényi, Imre; Malnasi-Csizmadia, Andras

2011-08-01

Our aim was to elucidate the physical background of internal friction of enzyme reactions by investigating the temperature dependence of internal viscosity. By rapid transient kinetic methods, we directly measured the rate constant of trypsin 4 activation, which is an interdomain conformational rearrangement, as a function of temperature and solvent viscosity. We found that the apparent internal viscosity shows an Arrhenius-like temperature dependence, which can be characterized by the activation energy of internal friction. Glycine and alanine mutations were introduced at a single position of the hinge of the interdomain region to evaluate how the flexibility of the hinge affects internal friction. We found that the apparent activation energies of the conformational change and the internal friction are interconvertible parameters depending on the protein flexibility. The more flexible a protein was, the greater proportion of the total activation energy of the reaction was observed as the apparent activation energy of internal friction. Based on the coupling of the internal and external movements of the protein during its conformational change, we constructed a model that quantitatively relates activation energy, internal friction, and protein flexibility.

Reaction of bromine and chlorine with phenolic compounds and natural organic matter extracts--Electrophilic aromatic substitution and oxidation.

PubMed

Criquet, Justine; Rodriguez, Eva M; Allard, Sebastien; Wellauer, Sven; Salhi, Elisabeth; Joll, Cynthia A; von Gunten, Urs

2015-11-15

Phenolic compounds are known structural moieties of natural organic matter (NOM), and their reactivity is a key parameter for understanding the reactivity of NOM and the disinfection by-product formation during oxidative water treatment. In this study, species-specific and/or apparent second order rate constants and mechanisms for the reactions of bromine and chlorine have been determined for various phenolic compounds (phenol, resorcinol, catechol, hydroquinone, phloroglucinol, bisphenol A, p-hydroxybenzoic acid, gallic acid, hesperetin and tannic acid) and flavone. The reactivity of bromine with phenolic compounds is very high, with apparent second order rate constants at pH 7 in the range of 10(4) to 10(7) M(-1) s(-1). The highest value was recorded for the reaction between HOBr and the fully deprotonated resorcinol (k = 2.1 × 10(9) M(-1) s(-1)). The reactivity of phenolic compounds is enhanced by the activating character of the phenolic substituents, e.g. further hydroxyl groups. With the data set from this study, the ratio between the species-specific rate constants for the reactions of chlorine versus bromine with phenolic compounds was confirmed to be about 3000. Phenolic compounds react with bromine or chlorine either by oxidation (electron transfer, ET) or electrophilic aromatic substitution (EAS) processes. The dominant process mainly depends on the relative position of the hydroxyl substituents and the possibility of quinone formation. While phenol, p-hydroxybenzoic acid and bisphenol A undergo EAS, hydroquinone, catechol, gallic acid and tannic acid, with hydroxyl substituents in ortho or para positions, react with bromine by ET leading to quantitative formation of the corresponding quinones. Some compounds (e.g. phloroglucinol) show both partial oxidation and partial electrophilic aromatic substitution and the ratio observed for the pathways depends on the pH. For the reaction of six NOM extracts with bromine, electrophilic aromatic substitution accounted for only 20% of the reaction, and for one NOM extract (Pony Lake fulvic acid) it accounted for <10%. This shows that for natural organic matter samples, oxidation (ET) is far more important than bromine incorporation (EAS). Copyright © 2015 Elsevier Ltd. All rights reserved.

Constitutive law for seismicity rate based on rate and state friction: Dieterich 1994 revisited.

NASA Astrophysics Data System (ADS)

Heimisson, E. R.; Segall, P.

2017-12-01

Dieterich [1994] derived a constitutive law for seismicity rate based on rate and state friction, which has been applied widely to aftershocks, earthquake triggering, and induced seismicity in various geological settings. Here, this influential work is revisited, and re-derived in a more straightforward manner. By virtue of this new derivation the model is generalized to include changes in effective normal stress associated with background seismicity. Furthermore, the general case when seismicity rate is not constant under constant stressing rate is formulated. The new derivation provides directly practical integral expressions for the cumulative number of events and rate of seismicity for arbitrary stressing history. Arguably, the most prominent limitation of Dieterich's 1994 theory is the assumption that seismic sources do not interact. Here we derive a constitutive relationship that considers source interactions between sub-volumes of the crust, where the stress in each sub-volume is assumed constant. Interactions are considered both under constant stressing rate conditions and for arbitrary stressing history. This theory can be used to model seismicity rate due to stress changes or to estimate stress changes using observed seismicity from triggered earthquake swarms where earthquake interactions and magnitudes are take into account. We identify special conditions under which influence of interactions cancel and the predictions reduces to those of Dieterich 1994. This remarkable result may explain the apparent success of the model when applied to observations of triggered seismicity. This approach has application to understanding and modeling induced and triggered seismicity, and the quantitative interpretation of geodetic and seismic data. It enables simultaneous modeling of geodetic and seismic data in a self-consistent framework. To date physics-based modeling of seismicity with or without geodetic data has been found to give insight into various processes related to aftershocks, VT and injection-induced seismicity. However, the role of various processes such as earthquake interactions and magnitudes and effective normal stress has been unclear. The new theory presented resolves some of the pertinent issues raised in the literature with application of the Dieterich 1994 model.

A dye-binding assay for measurement of the binding of Cu(II) to proteins.

PubMed

Wilkinson-White, Lorna E; Easterbrook-Smith, Simon B

2008-10-01

We analysed the theory of the coupled equilibria between a metal ion, a metal ion-binding dye and a metal ion-binding protein in order to develop a procedure for estimating the apparent affinity constant of a metal ion:protein complex. This can be done by analysing from measurements of the change in the concentration of the metal ion:dye complex with variation in the concentration of either the metal ion or the protein. Using experimentally determined values for the affinity constant of Cu(II) for the dye, 2-(5-bromo-2-pyridylaxo)-5-(N-propyl-N-sulfopropylamino) aniline (5-Br-PSAA), this procedure was used to estimate the apparent affinity constants for formation of Cu(II):transthyretin, yielding values which were in agreement with literature values. An apparent affinity constant for Cu(II) binding to alpha-synuclein of approximately 1 x 10(9)M(-1) was obtained from measurements of tyrosine fluorescence quenching by Cu(II). This value was in good agreement with that obtained using 5-Br-PSAA. Our analysis and data therefore show that measurement of changes in the equilibria between Cu(II) and 5-Br-PSAA by Cu(II)-binding proteins provides a general procedure for estimating the affinities of proteins for Cu(II).

Nucleation kinetics from metastable zone widths for sonocrystallization of l-phenylalanine.

PubMed

Hazi Mastan, T; Lenka, Maheswata; Sarkar, Debasis

2017-05-01

This study investigates the effect of ultrasound on metastable zone width (MSZW) during crystallization of l-phenylalanine from aqueous solution. The solubility of l-phenylalanine in water was measured gravimetrically in the temperature range of 293.15-333.15K. The MSZW was measured by conventional polythermal method for four different cooling rates at five different saturation temperatures in absence and presence of ultrasound. The MSZW increased with increase in cooling rates and decreased with increase in saturation temperature. The application of ultrasound considerably reduced the MSZW for all the experiments. The obtained MSZW data are analysed using four different approaches to calculate various nucleation parameters. In presence of ultrasound, the apparent nucleation order decreased and nucleation rate constant increased significantly. Copyright © 2016 Elsevier B.V. All rights reserved.

A Constant Rate of Spontaneous Mutation in DNA-Based Microbes

NASA Astrophysics Data System (ADS)

Drake, John W.

1991-08-01

In terms of evolution and fitness, the most significant spontaneous mutation rate is likely to be that for the entire genome (or its nonfrivolous fraction). Information is now available to calculate this rate for several DNA-based haploid microbes, including bacteriophages with single- or double-stranded DNA, a bacterium, a yeast, and a filamentous fungus. Their genome sizes vary by ≈6500-fold. Their average mutation rates per base pair vary by ≈16,000-fold, whereas their mutation rates per genome vary by only ≈2.5-fold, apparently randomly, around a mean value of 0.0033 per DNA replication. The average mutation rate per base pair is inversely proportional to genome size. Therefore, a nearly invariant microbial mutation rate appears to have evolved. Because this rate is uniform in such diverse organisms, it is likely to be determined by deep general forces, perhaps by a balance between the usually deleterious effects of mutation and the physiological costs of further reducing mutation rates.

MR imaging of apparent 3He gas transport in narrow pipes and rodent airways

NASA Astrophysics Data System (ADS)

Minard, Kevin R.; Jacob, Richard E.; Laicher, Gernot; Einstein, Daniel R.; Kuprat, Andrew P.; Corley, Richard A.

2008-10-01

High sensitivity makes hyperpolarized 3He an attractive signal source for visualizing gas flow with magnetic resonance (MR) imaging. Its rapid Brownian motion, however, can blur observed flow lamina and alter measured diffusion rates when excited nuclei traverse shear-induced velocity gradients during data acquisition. Here, both effects are described analytically, and predicted values for measured transport during laminar flow through a straight, 3.2-mm diameter pipe are validated using two-dimensional (2D) constant-time images of different binary gas mixtures. Results show explicitly how measured transport in narrow conduits is characterized by apparent values that depend on underlying gas dynamics and imaging time. In ventilated rats, this is found to obscure acquired airflow images. Nevertheless, flow splitting at airway branches is still evident and use of 3D vector flow mapping is shown to reveal surprising detail that highlights the correlation between gas dynamics and lung structure.

Thermokinetic comparison of trypan blue decolorization by free laccase and fungal biomass.

PubMed

Razak, N N A; Annuar, M S M

2014-03-01

Free laccase and fungal biomass from white-rot fungi were compared in the thermokinetics study of the laccase-catalyzed decolorization of an azo dye, i.e., Trypan Blue. The decolorization in both systems followed a first-order kinetics. The apparent first-order rate constant, k1', value increases with temperature. Apparent activation energy of decolorization was similar for both systems at ∼ 22 kJ mol(-1), while energy for laccase inactivation was 18 kJ mol(-1). Although both systems were endothermic, fungal biomass showed higher enthalpy, entropy, and Gibbs free energy changes for the decolorization compared to free laccase. On the other hand, free laccase showed reaction spontaneity over a wider range of temperature (ΔT = 40 K) as opposed to fungal biomass (ΔT = 15 K). Comparison of entropy change (ΔS) values indicated metabolism of the dye by the biomass.

The mathematical origins of the kinetic compensation effect: 2. The effect of systematic errors.

PubMed

Barrie, Patrick J

2012-01-07

The kinetic compensation effect states that there is a linear relationship between Arrhenius parameters ln A and E for a family of related processes. It is a widely observed phenomenon in many areas of science, notably heterogeneous catalysis. This paper explores mathematical, rather than physicochemical, explanations for the compensation effect in certain situations. Three different topics are covered theoretically and illustrated by examples. Firstly, the effect of systematic errors in experimental kinetic data is explored, and it is shown that these create apparent compensation effects. Secondly, analysis of kinetic data when the Arrhenius parameters depend on another parameter is examined. In the case of temperature programmed desorption (TPD) experiments when the activation energy depends on surface coverage, it is shown that a common analysis method induces a systematic error, causing an apparent compensation effect. Thirdly, the effect of analysing the temperature dependence of an overall rate of reaction, rather than a rate constant, is investigated. It is shown that this can create an apparent compensation effect, but only under some conditions. This result is illustrated by a case study for a unimolecular reaction on a catalyst surface. Overall, the work highlights the fact that, whenever a kinetic compensation effect is observed experimentally, the possibility of it having a mathematical origin should be carefully considered before any physicochemical conclusions are drawn.

Toward elimination of discrepancies between theory and experiment: The rate constant of the atmospheric conversion of SO3 to H2SO4

PubMed Central

Loerting, Thomas; Liedl, Klaus R.

2000-01-01

The hydration rate constant of sulfur trioxide to sulfuric acid is shown to depend sensitively on water vapor pressure. In the 1:1 SO3-H2O complex, the rate is predicted to be slower by about 25 orders of magnitude compared with laboratory results [Lovejoy, E. R., Hanson, D. R. & Huey, L. G. (1996) J. Phys. Chem. 100, 19911–19916; Jayne, J. T., Pöschl, U., Chen, Y.-m., Dai, D., Molina, L. T., Worsnop, D. R., Kolb, C. E. & Molina, M. J. (1997) J. Phys. Chem. A 101, 10000–10011]. This discrepancy is removed mostly by allowing a second and third water molecule to participate. An asynchronous water-mediated double proton transfer concerted with the nucleophilic attack and a double proton transfer accompanied by a transient H3O+ rotation are predicted to be the fastest reaction mechanisms. Comparison of the predicted negative apparent “activation” energies with the experimental finding indicates that in our atmosphere, different reaction paths involving two and three water molecules are taken in the process of forming sulfate aerosols and consequently acid rain. PMID:10922048

Slow and fast motion of cracks in inelastic solids. Part 1: Slow growth of cracks in a rate sensitive tresca solid. Part 2: Dynamic crack represented by the Dugdale model

NASA Technical Reports Server (NTRS)

Wnuk, M. P.; Sih, G. C.

1972-01-01

An extension is proposed of the classical theory of fracture to viscoelastic and elastic-plastic materials in which the plasticity effects are confined to a narrow band encompassing the crack front. It is suggested that the Griffith-Irwin criterion of fracture, which requires that the energy release rate computed for a given boundary value problem equals the critical threshold, ought to be replaced by a differential equation governing the slow growth of a crack prior to the onset of rapid propagation. A new term which enters the equation of motion in the dissipative media is proportional to the energy lost within the end sections of the crack, and thus reflects the extent of inelastic behavior of a solid. A concept of apparent surface energy is introduced to account for the geometry dependent and the rate dependent phenomena which influence toughness of an inelastic solid. Three hypotheses regarding the condition for fracture in the subcritical range of load are compared. These are: (1) constant fracture energy (Cherepanov), (2) constant opening displacement at instability (Morozov) and (3) final stretch criterion (Wnuk).

Inhibition of hydroxyl radical reaction with aromatics by dissolved natural organic matter

USGS Publications Warehouse

Lindsey, M.E.; Tarr, M.A.

2000-01-01

Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compound molecules bound to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanism for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently firstorder in pyrene to one that was apparently secondorder in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compounds molecules bounds to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanisms for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently first-order in pyrene to one that was apparently second-order in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.

Acetylcholinesterase-catalyzed acetate - water oxygen exchange studied by /sup 13/C-NMR

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

Van Etten, R.L.; Dayton, B.; Cortes, S.

1986-05-01

The kinetics of the oxygen exchange reaction between (l-/sup 13/C,/sup 18/O/sub 2/)acetate and H/sub 2//sup 16/O catalyzed by homogeneous acetyl-cholinesterase from the electric eel, Electrophorus electricus, was studied using the /sup 18/O-isotope-induced shift on /sup 13/C-nuclear magnetic resonance spectra. Pseudo-first-order rate constants for the exchange reactions were determined at pH values from 4.5 to 8. The exchange reaction exhibits a maximum at pH 5.8. The apparent catalytic rate constant for the exchange reaction is 10/sup 2/ to 10/sup 4/ times smaller than that for the deacylation of the acetyl-enzyme intermediate over the pH range tested. Oxygen exchange occurs by amore » random sequential pathway rather than by multiple (coupled) exchange. The inhibition of acetylcholinesterase by sodium acetate showed a sigmoidal dependence on pH, with K/sub i/ increasing 2.5 orders of magnitude over the pH range. Protonation of an active site residue having an apparent pKa of 6.8 is associated with an increase in acetate binding. Deacylation also exhibits a sigmoidal dependence on (H/sup +/). The experimental data fits titration curves with inflection points at 5.0 +/- 0.3 and 6.7 +/-0.1. Results support the role of histidine in acetylation of the active site serine, but the conjugate base of another active site residue with a pKa of 5.0 appears necessary for maximal catalytic activity in both the deacylation and exchange reactions.« less

Possible applications of time domain reflectometry in planetary exploration missions

NASA Technical Reports Server (NTRS)

Heckendorn, S.

1982-01-01

The use of a time domain reflectometer (TDR) for planetary exploration is considered. Determination of the apparent dielectric constant and hence, the volumetric water content of frozen and unfrozen soils using the TDR is described. Earth-based tests were performed on a New York state sandy soil and a Wyoming Bentonite. Use of both a cylindrical coaxial transmission line and a parallel transmission line as probes was evaluated. The water content of the soils was varied and the apparent dielectric constant measured in both frozen and unfrozen states. Advantages and disadvantages of the technique are discussed.

Trehalose delays the reversible but not the irreversible thermal denaturation of cutinase.

PubMed

Baptista, R P; Cabral, J M; Melo, E P

2000-12-20

The effect of trehalose (0.5 M) on the thermal stability of cutinase in the alkaline pH range was studied. The thermal unfolding induced by increasing temperature was analyzed in the absence and in the presence of trehalose according to a two-state model (which assumes that only the folded and unfolded states of cutinase were present). Trehalose delays the reversible unfolding. The midpoint temperature of the unfolding transition (Tm) increases by 4.0 degrees C and 2. 6 degrees C at pH 9.2 and 10.5, respectively, in the presence of trehalose. At pH 9.2 the thermal unfolding occurs at higher temperatures (Tm is 52.6 degrees C compared to 42.0 degrees C at pH 10.5) and a refolding yield of around 80% was obtained upon cooling. This pH value was chosen to study the irreversible inactivation (long-term stability) of cutinase. Temperatures in the transition range from folded to unfolded state were selected and the rate constants of irreversible inactivation determined. Inactivation followed first-order kinetics and trehalose reduced the observed rate constants of inactivation, pointing to a stabilizing effect on the irreversible inactivation step of thermal denaturation. However, if the contribution of reversible unfolding on the irreversible inactivation of cutinase was taken into account, i.e., considering the fraction of cutinase molecules in the reversible unfolded conformation, the intrinsic rate constants can be calculated. Based on the intrinsic rate constants it was concluded that trehalose does not delay the irreversible inactivation. This conclusion was further supported by comparing the activation energy of the irreversible inactivation in the absence and in the presence of trehalose. The apparent activation energy in the absence and in the presence of trehalose were 67 and 99 Kcal/mol, respectively. The activation energy calculated from intrinsic rate constants was higher in the absence (30 Kcal/mol) than in the presence of trehalose (16 Kcal/mol), showing that kinetics of the irreversible inactivation step increased in the presence of trehalose. In fact, trehalose stabilized only the reversible step of thermal denaturation of cutinase.

Trends in frequency of type 2 diabetes in Mexico and its relationship to dietary patterns and contextual factors.

PubMed

Soto-Estrada, Guadalupe; Moreno Altamirano, Laura; García-García, Juan José; Ochoa Moreno, Iván; Silberman, Martín

To analyse the evolution of the frequency of type 2 diabetes (T2D) and its relationship to eating patterns in Mexico from 1961 to 2013, and the Gini coefficient, Human Development Index (HDI) and Gross Domestic Product (GDP). Mexico ranked sixth in world prevalence of diabetes in 2015 with an estimated 11.4 million Mexicans affected. Using data from the Balance Sheets Food published by the Food and Agriculture Organization of the United Nations (FAO), the means of apparent food consumption (kcal/person/day) were grouped by decades. Data for mortality rate for diabetes were obtained from 1990 until 2015. Spearman's correlation coefficient was calculated between the diabetes mellitus mortality rate and all food groups. Pearson's correlation explored the relationship between socio economic indicators and the prevalence of T2D diabetes. The mortality rate for T2D has increased over the last decades. An increase of 647.9kcal/person/day in apparent food consumption was observed. Cereal and legume consumption decreased, while apparent sugar, animal food and animal fat and vegetable oil consumption increased substantially. HDI and GDP showed a directly proportional relationship to diabetes. Spearman's correlation coefficient was statistically significant only for sugar. The Gini coefficient suggests that in lower inequalities there is an increased frequency of diabetes. The increase in the mortality rate of type 2 diabetes was constant during the study period, which coincides with the increase in energy density of Mexican eating patterns from 1961 to 2013. The higher the Gini coefficient, HDI and GDP, the higher the mortality observed for diabetes. Copyright © 2017 SESPAS. Publicado por Elsevier España, S.L.U. All rights reserved.

Protein A chromatography increases monoclonal antibody aggregation rate during subsequent low pH virus inactivation hold

PubMed Central

Mazzer, Alice R.; Perraud, Xavier; Halley, Jennifer; O’Hara, John; Bracewell, Daniel G.

2015-01-01

Protein A chromatography is a near-ubiquitous method of mAb capture in bioprocesses. The use of low pH buffer for elution from protein A is known to contribute to product aggregation. Yet, a more limited set of evidence suggests that low pH may not be the sole cause of aggregation in protein A chromatography, rather, other facets of the process may contribute significantly. This paper presents a well-defined method for investigating this problem. An IgG4 was incubated in elution buffer after protein A chromatography (typical of the viral inactivation hold) and the quantity of monomer in neutralised samples was determined by size exclusion chromatography; elution buffers of different pH values predetermined to induce aggregation of the IgG4 were used. Rate constants for monomer decay over time were determined by fitting exponential decay functions to the data. Similar experiments were implemented in the absence of a chromatography step, i.e. IgG4 aggregation at low pH. Rate constants for aggregation after protein A chromatography were considerably higher than those from low pH exposure alone; a distinct shift in aggregation rates was apparent across the pH range tested. PMID:26346187

Bacteriocin Production with Lactobacillus amylovorus DCE 471 Is Improved and Stabilized by Fed-Batch Fermentation

PubMed Central

Callewaert, Raf; De Vuyst, Luc

2000-01-01

Amylovorin L471 is a small, heat-stable, and hydrophobic bacteriocin produced by Lactobacillus amylovorus DCE 471. The nutritional requirements for amylovorin L471 production were studied with fed-batch fermentations. A twofold increase in bacteriocin titer was obtained when substrate addition was controlled by the acidification rate of the culture, compared with the titers reached with constant substrate addition or pH-controlled batch cultures carried out under the same conditions. An interesting feature of fed-batch cultures observed under certain culture conditions (constant feed rate) is the apparent stabilization of bacteriocin activity after obtaining maximum production. Finally, a mathematical model was set up to simulate cell growth, glucose and complex nitrogen source consumption, and lactic acid and bacteriocin production kinetics. The model showed that bacterial growth was dependent on both the energy and the complex nitrogen source. Bacteriocin production was growth associated, with a simultaneous bacteriocin adsorption on the producer cells dependent on the lactic acid accumulated and hence the viability of the cells. Both bacteriocin production and adsorption were inhibited by high concentrations of the complex nitrogen source. PMID:10653724

Photostabilization of ascorbic acid with citric acid, tartaric acid and boric acid in cream formulations.

PubMed

Ahmad, I; Ali Sheraz, M; Ahmed, S; Shad, Z; Vaid, F H M

2012-06-01

This study involves the evaluation of the effect of certain stabilizers, that is, citric acid (CT), tartaric acid (TA) and boric acid (BA) on the degradation of ascorbic acid (AH(2) ) in oil-in-water cream formulations exposed to the UV light and stored in the dark. The apparent first-order rate constants (0.34-0.95 × 10(-3) min(-1) in light, 0.38-1.24 × 10(-2) day(-1) in dark) for the degradation reactions in the presence of the stabilizers have been determined. These rate constants have been used to derive the second-order rate constants (0.26-1.45 × 10(-2) M(-1) min(-1) in light, 3.75-8.50 × 10(-3) M(-1) day(-1) in dark) for the interaction of AH(2) and the individual stabilizers. These stabilizers are effective in causing the inhibition of the rate of degradation of AH(2) both in the light and in the dark. The inhibitory effect of the stabilizers is in the order of CT > TA > BA. The rate of degradation of AH(2) in the presence of these stabilizers in the light is about 120 times higher than that in the dark. This could be explained on the basis of the deactivation of AH(2) -excited triplet state by CT and TA and by the inhibition of AH(2) degradation through complex formation with BA. AH(2) leads to the formation of dehydroascorbic acid (A) by chemical and photooxidation in cream formulations. © 2012 The Authors. ICS © 2012 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Kinetics of aqueous chlorination of some pharmaceuticals and their elimination from water matrices.

PubMed

Acero, Juan L; Benitez, F Javier; Real, Francisco J; Roldan, Gloria

2010-07-01

Apparent rate constants for the reactions of four selected pharmaceutical compounds (metoprolol, naproxen, amoxicillin, and phenacetin) with chlorine in ultra-pure (UP) water were determined as a function of the pH. It was found that amoxicillin (in the whole pH range 3-12), and naproxen (in the low pH range 2-4) presented high reaction rates, while naproxen (in the pH range 5-9), and phenacetin and metoprolol (in the pH range 2.5-12 for phenacetin, and 3-10 for metoprolol) followed intermediate and slow reaction rates. A mechanism is proposed for the chlorination reaction, which allowed the evaluation of the intrinsic rate constants for the elementary reactions of the ionized and un-ionized species of each selected pharmaceutical with chlorine. An excellent agreement is obtained between experimental and calculated rate constants by this mechanism.The elimination of these substances in several waters (a groundwater, a surface water from a public reservoir, and two effluents from municipal wastewater treatment plants) was also investigated at neutral pH. The efficiency of the chlorination process with respect to the pharmaceuticals elimination and the formation THMs was also established. It is generally observed that the increasing presence of organic and inorganic matter in the water matrices demand more oxidant agent (chlorine), and therefore, less chlorine is available for the oxidation of these compounds. Finally, half-life times and oxidant exposures (CT) required for the removal of 99% of the four pharmaceuticals are also evaluated. These parameters are useful for the establishment of safety chlorine doses in oxidation or disinfection stages of pharmaceuticals in treatment plants.

Simultaneous pharmacodynamic analysis of the lag and bactericidal phases exhibited by beta-lactams against Escherichia coli.

PubMed Central

Li, R C

1996-01-01

Antibiotic-bacterium interactions are complex in nature. In many cases, bacterial killing does not commence immediately after the addition of an antibiotic, and a lag period is observed. Antibiotic permeation and/or the intermediate steps that exist between antibiotic-receptor binding and expression of cell death are two major possible causes for such lag period. This study was primarily designed to determine the relationship, if any, between antibiotic concentrations and the lag periods by a modeling approach. Short-term time-kill studies were conducted for amoxicillin, ampicillin, penicillin-G, oxacillin, and dicloxacillin against Escherichia coli. In conjunction with the use of a saturable rate model to describe the concentration-dependent killing process, a first-order induction (initiation) rate constant was used to characterize the delay in bacterial killing during the lag period. For all of the beta-lactams tested, parameters describing the bactericidal effect suggest that amoxicillin and ampicillin were much more potent than oxacillin and dicloxacillin. The induction rate constant estimates for both ampicillin and amoxicillin were found to relate linearly to concentrations. Nevertheless, these induction rate constant estimates were lower for penicillin-G, oxacillin, and dicloxacillin and increased nonlinearly with concentrations until an apparent plateau was observed. These findings support the hypothesis that the permeation process is potentially a rate-limiting step for the rapid bactericidal beta-lactams such as ampicillin and amoxicillin. However, as suggested by previous observations of the various morphological changes induced by beta-lactams, the contribution of the steps following antibiotic-receptor complex formation to the lag period might be significant for the less bactericidal antibiotics such as oxacillin and dicloxacillin. Findings from the present modeling approach can potentially be used to guide future bench experimentation. PMID:8891135

Ab initio calculations of deep-level carrier nonradiative recombination rates in bulk semiconductors.

PubMed

Shi, Lin; Wang, Lin-Wang

2012-12-14

Nonradiative carrier recombination is of both applied and fundamental interest. Here a novel algorithm is introduced to calculate such a deep level nonradiative recombination rate using the ab initio density functional theory. This algorithm can calculate the electron-phonon coupling constants all at once. An approximation is presented to calculate the phonon modes for one impurity in a large supercell. The neutral Zn impurity site together with a N vacancy is considered as the carrier-capturing deep impurity level in bulk GaN. Its capture coefficient is calculated as 5.57 × 10(-10)cm(3)/s at 300 K. We found that there is no apparent onset of such a nonradiative process as a function of temperature.

The effects of MgADP on cross-bridge kinetics: a laser flash photolysis study of guinea-pig smooth muscle.

PubMed Central

Nishiye, E; Somlyo, A V; Török, K; Somlyo, A P

1993-01-01

1. The effects of MgADP on cross-bridge kinetics were investigated using laser flash photolysis of caged ATP (P3-1(2-nitrophenyl) ethyladenosine 5'-triphosphate), in guinea-pig portal vein smooth muscle permeabilized with Staphylococcus aureus alpha-toxin. Isometric tension and in-phase stiffness transitions from rigor state were monitored upon photolysis of caged ATP. The estimated concentration of ATP released from caged ATP by high-pressure liquid chromatography (HPLC) was 1.3 mM. 2. The time course of relaxation initiated by photolysis of caged ATP in the absence of Ca2+ was well fitted during the initial 200 ms by two exponential functions with time constants of, respectively, tau 1 = 34 ms and tau 2 = 1.2 s and relative amplitudes of 0.14 and 0.86. Multiple exponential functions were needed to fit longer intervals; the half-time of the overall relaxation was 0.8 s. The second order rate constant for cross-bridge detachment by ATP, estimated from the rate of initial relaxation, was 0.4-2.3 x 10(4) M-1 s-1. 3. MgADP dose dependently reduced both the relative amplitude of the first component and the rate constant of the second component of relaxation. Conversely, treatment of muscles with apyrase, to deplete endogenous ADP, increased the relative amplitude of the first component. In the presence of MgADP, in-phase stiffness decreased during force maintenance, suggesting that the force per cross-bridge increased. The apparent dissociation constant (Kd) of MgADP for the cross-bridge binding site, estimated from its concentration-dependent effect on the relative amplitude of the first component, was 1.3 microM. This affinity is much higher than the previously reported values (50-300 microM for smooth muscle; 18-400 microM for skeletal muscle; 7-10 microM for cardiac muscle). It is possible that the high affinity reflects the properties of a state generated during the co-operative reattachment cycle, rather than that of the rigor bridge. 4. The rate constant of MgADP release from cross-bridges, estimated from its concentration-dependent effect on the rate constant of the second (tau 2) component, was 0.35-7.7 s-1. To the extent that reattachment of cross-bridges could slow relaxation even during the initial 200 ms, this rate constant may be an underestimate. 5. Inorganic phosphate (Pi, 30 mM) did not affect the rate of relaxation during the initial approximately 50 ms, but accelerated the slower phase of relaxation, consistent with a cyclic cross-bridge model in which Pi increases the proportion of cross-bridges in detached ('weakly bound') states.(ABSTRACT TRUNCATED AT 400 WORDS) Images Fig. 1 PMID:8487195

The daily rhythm of body temperature, heart and respiratory rate in newborn dogs.

PubMed

Piccione, Giuseppe; Giudice, Elisabetta; Fazio, Francesco; Mortola, Jacopo P

2010-08-01

We asked whether, during the postnatal period, the daily patterns of body temperature (Tb), heart rate (HR) and breathing frequency (f) begin and develop in synchrony. To this end, measurements of HR, f and Tb were performed weekly, on two consecutive days, for the first two postnatal months on puppies of three breeds of dogs (Rottweiler, Cocker Spaniel and Carlino dogs) with very different birth weights and postnatal growth patterns. Ambient conditions and feeding habits were constant for all puppies. The results indicated that (1) the 24-h average Tb increased and average HR and f decreased with growth, (2) the daily rhythms in Tb were apparent by 4 weeks, irrespective of the puppy's growth pattern, (3) the daily rhythm of Tb in the puppy was not necessarily following that of the mother; in fact, it could anticipate it. (4) The daily rhythms in HR and f were not apparent for the whole study period. We conclude that in neonatal dogs the onset of the daily rhythms of Tb has no obvious relationship with body size or rate of growth and is not cued by the maternal Tb rhythm. The daily rhythms of HR and f do not appear before 2 months of age. Hence, they are not in synchrony with those of Tb.

The influence of amorphization methods on the apparent solubility and dissolution rate of tadalafil.

PubMed

Wlodarski, K; Sawicki, W; Paluch, K J; Tajber, L; Grembecka, M; Hawelek, L; Wojnarowska, Z; Grzybowska, K; Talik, E; Paluch, M

2014-10-01

This study for the first time investigates the solubility and dissolution rate of amorphous tadalafil (Td)--a poorly water soluble chemical compound which is commonly used for treating the erectile dysfunction. To convert the crystalline form of Td drug to its amorphous counterpart we have employed most of the commercially available amorphization techniques i.e. vitrification, cryogenic grinding, ball milling, spray drying, freeze drying and antisolvent precipitation. Among the mentioned methods only quenched cooling of the molten sample was found to be an inappropriate method of Td amorphization. This is due to the thermal decomposition of Td above 200°C, as proved by the thermogravimetric analysis (TGA). Disordered character of all examined samples was confirmed using differential scanning calorimetry (DSC) and X-ray powder diffraction (PXRD). In the case of most amorphous powders, the largest 3-fold increase of apparent solubility was observed after 5 min, indicating their fast recrystallization in water. On the other hand, the partially amorphous precipitate of Td and hypromellose enhanced the solubility of Td approximately 14 times, as compared with a crystalline substance, which remained constant for half an hour. Finally, disk intrinsic dissolution rate (DIDR) of amorphous forms of Td was also examined. Copyright © 2014 Elsevier B.V. All rights reserved.

Diclofenac removal from water with ozone and activated carbon.

PubMed

Beltrán, Fernando J; Pocostales, Pablo; Alvarez, Pedro; Oropesa, Ana

2009-04-30

Diclofenac (DCF) has been treated in water with ozone in the presence of various activated carbons. Activated carbon-free ozonation or single ozonation leads to a complete degradation of DCF in less than 15 min while in the presence of activated carbons higher degradation rates of TOC and DCF are noticeably achieved. Among the activated carbons used, P110 Hydraffin was found the most suitable for the catalytic ozonation of DCF. The influence of pH was also investigated. In the case of the single ozonation the increasing pH slightly increases the TOC removal rate. This effect, however, was not so clear in the presence of activated carbons where the influence of the adsorption process must be considered. Ecotoxicity experiments were performed, pointing out that single ozonation reduces the toxicity of the contaminated water but catalytic ozonation improved those results. As far as kinetics is concerned, DCF is removed with ozone in a fast kinetic regime and activated carbon merely acts as a simple adsorbent. However, for TOC removal the ozonation kinetic regime becomes slow. In the absence of the adsorbent, the apparent rate constant of the mineralization process was determined at different pH values. On the other hand, determination of the rate constant of the catalytic reaction over the activated carbon was not possible due to the effect of mass transfer resistances that controlled the process rate at the conditions investigated.

Escherichia coli promoter sequences predict in vitro RNA polymerase selectivity.

PubMed

Mulligan, M E; Hawley, D K; Entriken, R; McClure, W R

1984-01-11

We describe a simple algorithm for computing a homology score for Escherichia coli promoters based on DNA sequence alone. The homology score was related to 31 values, measured in vitro, of RNA polymerase selectivity, which we define as the product KBk2, the apparent second order rate constant for open complex formation. We found that promoter strength could be predicted to within a factor of +/-4.1 in KBk2 over a range of 10(4) in the same parameter. The quantitative evaluation was linked to an automated (Apple II) procedure for searching and evaluating possible promoters in DNA sequence files.

Uniqueness of large positive solutions

NASA Astrophysics Data System (ADS)

López-Gómez, Julián; Maire, Luis

2017-08-01

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

Kinetic study of the oxidation of 4-hydroxyanisole catalyzed by tyrosinase.

PubMed

Espín, J C; Varón, R; Tudela, J; García-Cánovas, F

1997-05-01

Despite the importance of the substrate 4-hydroxyanisole in melanoma therapy, the kinetics of its oxidation catalyzed by tyrosinase has never been properly characterized. This approach is reported here for the first time. The applicability to 4-hydroxyanisole of the reaction mechanism of tyrosinase previously proposed for other monophenols has been corroborated. The Michaelis constant for the oxidation of 4-hydroxyanisole catalyzed by mushroom tyrosinase was (62 +/- 1.5) microM at pH 7 and increased when the pH decreased, reaching a value of (195 +/- 5) microM at pH 5.5. However the maximum steady-state rate, whose value was (0.54 +/- 0.01) microM/min, did not change with the pH. The apparent catalytic constant was (184 +/- 5) s-1, around twenty three times higher than that previously described for L-tyrosine (8 s-1).

Spin relaxation measurements of electrostatic bias in intermolecular exploration

NASA Astrophysics Data System (ADS)

Teng, Ching-Ling; Bryant, Robert G.

2006-04-01

We utilize the paramagnetic contribution to proton spin-lattice relaxation rate constants induced by freely diffusing charged paramagnetic centers to investigate the effect of charge on the intermolecular exploration of a protein by the small molecule. The proton NMR spectrum provided 255 resolved resonances that report how the explorer molecule local concentration varies with position on the surface. The measurements integrate over local dielectric constant variations, and, in principle, provide an experimental characterization of the surface free energy sampling biases introduced by the charge distribution on the protein. The experimental results for ribonuclease A obtained using positive, neutral, and negatively charged small nitroxide radicals are qualitatively similar to those expected from electrostatic calculations. However, while systematic electrostatic trends are apparent, the three different combinations of the data sets do not yield internally consistent values for the electrostatic contribution to the intermolecular free energy. We attribute this failure to the weakness of the electrostatic sampling bias for charged nitroxides in water and local variations in effective translational diffusion constant at the water-protein interface, which enters the nuclear spin relaxation equations for the nitroxide-proton dipolar coupling.

Measurement of Apparent Thermal Conductivity of JSC-1A Under Ambient Pressure

NASA Technical Reports Server (NTRS)

Yuan, Zeng-Guang; Kleinhenz, Julie E.

2011-01-01

The apparent thermal conductivity of JSC-1A lunar regolith simulant was measured experimentally using a cylindrical apparatus. Eleven thermocouples were embedded in the simulant bed to obtain the steady state temperature distribution at various radial, axial, and azimuthal locations. The high aspect ratio of a cylindrical geometry was proven to provide a one-dimensional, axisymmetric temperature field. A test series was performed at atmospheric pressure with varying heat fluxes. The radial temperature distribution in each test fit a logarithmic function, indicating a constant thermal conductivity throughout the soil bed. However, thermal conductivity was not constant between tests at different heat fluxes. This variation is attributed to stresses created by thermal expansion of the simulant particles against the rigid chamber wall. Under stress-free conditions (20 deg C), the data suggest a temperature independent apparent conductivity of 0.1961 +/- 0.0070 W/m/ deg C

Influence of pH and ionic strength on electrostatic properties of ferredoxin, FNR, and hydrogenase and the rate constants of their interaction

NASA Astrophysics Data System (ADS)

Diakonova, A. N.; Khrushchev, S. S.; Kovalenko, I. B.; Riznichenko, G. Yu; Rubin, A. B.

2016-10-01

Ferredoxin (Fd) protein transfers electrons from photosystem I (PSI) to ferredoxin:NADP+-reductase (FNR) in the photosynthetic electron transport chain, as well as other metabolic pathways. In some photosynthetic organisms including cyanobacteria and green unicellular algae under anaerobic conditions Fd transfers electrons not only to FNR but also to hydrogenase—an enzyme which catalyzes reduction of atomic hydrogen to H2. One of the questions posed by this competitive relationship between proteins is which characteristics of thylakoid stroma media allow switching of the electron flow between the linear path PSI-Fd-FNR-NADP+ and the path PSI-Fd-hydrogenase-H2. The study was conducted using direct multiparticle simulation approach. In this method protein molecules are considered as individual objects that experience Brownian motion and electrostatic interaction with the surrounding media and each other. Using the model we studied the effects of pH and ionic strength (I) upon complex formation between ferredoxin and FNR and ferredoxin and hydrogenase. We showed that the rate constant of Fd-FNR complex formation is constant in a wide range of physiologically significant pH values. Therefore it can be argued that regulation of FNR activity doesn’t involve pH changes in stroma. On the other hand, in the model rate constant of Fd-hydrogenase interaction dramatically depends upon pH: in the range 7-9 it increases threefold. It may seem that because hydrogenase reduces protons it should be more active when pH is acidic. Apparently, regulation of hydrogenase’s affinity to both her reaction partners (H+ and Fd) is carried out by changes in its electrostatic properties. In the dark, the protein is inactive and in the light it is activated and starts to interact with both Fd and H+. Therefore, we can conclude that in chloroplasts the rate of hydrogen production is regulated by pH through the changes in the affinity between hydrogenase and ferredoxin.

Population pharmacokinetics of olmesartan following oral administration of its prodrug, olmesartan medoxomil: in healthy volunteers and hypertensive patients.

PubMed

Yoshihara, Kazutaka; Gao, Yuying; Shiga, Hiroshi; Wada, D Russell; Hisaoka, Masafumi

2005-01-01

Olmesartan medoxomil (CS-866) is a new orally active angiotensin II receptor antagonist that is highly selective for the AT1 receptor subtype. To develop a population pharmacokinetic model for olmesartan (RNH-6270), the active metabolite of olmesartan medoxomil, in healthy volunteers and hypertensive patients, and to evaluate effects of covariates on the apparent oral clearance (CL/F), with particular emphasis on the effect of race. Retrospective analysis of data from 12 phase I-III trials in the US, Europe and Japan. Eighty-nine healthy volunteers and 383 hypertensive patients. Nonlinear mixed-effects modelling was used to evaluate 7911 olmesartan plasma sample concentrations. The covariates included age, bodyweight, sex, race (Westerners [including Caucasians and Hispanics] versus Japanese), patient status (hypertensive patients versus healthy volunteers), serum creatinine level as an index of renal function and serum chemistry data as indices of hepatic function. The pharmacokinetic data of olmesartan were well described by a two-compartment linear model with first-order absorption and an absorption lag-time, parameterised in terms of CL/F (6.66 L/h for a typical male Western hypertensive patient), absorption rate constant (1.46h-1), elimination rate constant (0.193h-1), rate constant from the central to peripheral compartment (0.061h-1), rate constant from the peripheral to central compartment (0.079h-1) and absorption lag-time (0.427h). Analysis of covariates showed that age, bodyweight, sex, patient status and renal function were factors influencing the clearance of olmesartan. The population pharmacokinetic analysis of olmesartan showed that: (i) severe renal impairment (serum creatinine >265 micromol/L [approximately 3 mg/dL]) could cause a clearance decrease of > or =30%; (ii) older age, lower bodyweight and being female were determinants of lower clearance but their effects on olmesartan clearance were within 20%; (iii) no statistically significant difference in clearance was found between Westerners and Japanese.

Kinetics of thorium and particle cycling along the U.S. GEOTRACES North Atlantic Transect

NASA Astrophysics Data System (ADS)

Lerner, Paul; Marchal, Olivier; Lam, Phoebe J.; Buesseler, Ken; Charette, Matthew

2017-07-01

The high particle reactivity of thorium has resulted in its widespread use in tracing processes impacting marine particles and their chemical constituents. The use of thorium isotopes as tracers of particle dynamics, however, largely relies on our understanding of how the element scavenges onto particles. Here, we estimate apparent rate constants of Th adsorption (k1), Th desorption (k-1), bulk particle degradation (β-1), and bulk particle sinking speed (w) along the water column at 11 open-ocean stations occupied during the GEOTRACES North Atlantic Section (GA03). First, we provide evidence that the budgets of Th isotopes and particles at these stations appear to be generally dominated by radioactive production and decay sorption reactions, particle degradation, and particle sinking. Rate parameters are then estimated by fitting a Th and particle cycling model to data of dissolved and particulate 228,230,234Th, 228Ra, particle concentrations, and 234,238U estimates based on salinity, using a nonlinear programming technique. We find that the adsorption rate constant (k1) generally decreases with depth across the section: broadly, the time scale 1 /k1 averages 1.0 yr in the upper 1000 m and (1.4-1.5) yr below. A positive relationship between k1 and particle concentration (P) is found, i.e., k1 ∝Pb , where b ≥ 1 , consistent with the notion that k1 increases with the number of surface sites available for adsorption. The rate constant ratio, K =k1 / (k-1 +β-1) , which measures the collective influence of rate parameters on Th scavenging, averages 0.2 for most stations and most depths. We clarify the conditions under which K / P is equivalent to the distribution coefficient, KD, test that the conditions are met at the stations, and find that K / P decreases with P, in line with a particle concentration effect (dKD / dP < 0). In contrast to the influence of colloids as envisioned by the Brownian pumping hypothesis, we provide evidence that the particle concentration effect arises from the joint effect of P on the rate constants for thorium attachment to, and detachment from, particles.

Terminal base pairs of oligodeoxynucleotides: imino proton exchange and fraying.

PubMed

Nonin, S; Leroy, J L; Guéron, M

1995-08-22

We have estimated the dissociation constant of the terminal base pairs of the B-DNA duplexes formed by 5'-d(CGCGATCGCG) and 5'-d(TAGCGCTA) by two methods, one based on the change in imino proton chemical shift with temperature and the other on the apparent pK shift of the imino proton, as monitored by the change in chemical shift of aromatic protons. These methods do not rely on imino proton exchange, whose rate was also measured. (1) The effect of ammonia on the imino proton exchange rate of the terminal pair of the 5'-d(CGCGATCGCG) duplex is 67 times less than on the isolated nucleoside. This provides an upper limit on the exchange rate from the closed pair. In fact, the effect is just as predicted from the dissociation constant, assuming that there is no exchange at all from the closed pair and that, as has been argued previously, external catalysts act on the open state as they do on the isolated nucleoside. The inhibition of catalyzed proton exchange in the closed pair, despite exposure of one face of the pair to solvent, is a new feature of the exchange process. It will allow determination of the dissociation constant of terminal pairs from the exchange rate. (2) Intrinsic catalysis of proton exchange is less efficient for the terminal pair than for an internal one. A possible explanation is that proton transfer across the water bridge responsible for intrinsic catalysis is slower, as expected if the open-state separation of the bases is larger in a terminal pair. This observation may lead to a direct method for the study of fraying. (3) At 0 degrees C, the dissociation constant of the second pair of the 5'-d(CGCGATCGCG) duplex is close to the square of the constant for the terminal pair, as predicted from a simple model of fraying. The enthalpy and entropy of opening of the terminal pairs may be compared with those of nearest neighbor interactions derived from calorimetry [Breslauer, K. J., et al. (1986) Proc. Natl. Acad. Sci. U.S.A. 83, 3746-3750].

Investigation into adsorption and photocatalytic degradation of gaseous benzene in an annular fluidized bed photocatalytic reactor.

PubMed

Geng, Qijin; Tang, Shankang; Wang, Lintong; Zhang, Yunchen

2015-01-01

The adsorption and photocatalytic degradation of gaseous benzene were investigated considering the operating variables and kinetic mechanism using nano-titania agglomerates in an annular fluidized bed photocatalytic reactor (AFBPR) designed. The special adsorption equilibrium constant, adsorption active sites, and apparent reaction rate coefficient of benzene were determined by linear regression analysis at various gas velocities and relative humidities (RH). Based on a series of photocatalytic degradation kinetic equations, the influences of operating variables on degradation efficiency, apparent reaction rate coefficient and half-life were explored. The findings indicated that the operating variables have obviously influenced the adsorption/photocatalytic degradation and corresponding kinetic parameters. In the photocatalytic degradation process, the relationship between photocatalytic degradation efficiency and RH indicated that water molecules have a dual-function which was related to the structure characteristics of benzene. The optimal operating conditions for photocatalytic degradation of gaseous benzene in AFBPR were determined as the fluidization number at 1.9 and RH required related to benzene concentration. This investigation highlights the importance of controlling RH and benzene concentration in order to obtain the desired synergy effect in photocatalytic degradation processes.

Degradation rate of lyophilized insulin, exhibiting an apparent Arrhenius behavior around glass transition temperature regardless of significant contribution of molecular mobility.

PubMed

Yoshioka, Sumie; Miyazaki, Tamaki; Aso, Yukio

2006-12-01

The relative influences of chemical activation energy and molecular mobility in determining chemical reactivity were evaluated for insulin lyophilized with alpha,beta-poly(N-hydroxyethyl)-L-aspartamide (PHEA), and compared with that for insulin lyophilized with trehalose, which had been found to have the ability to decrease the molecular mobility of insulin at low humidity. The ratio of the observed rate constant k(obs) to the chemical activation energy-controlled rate constant k(act) (k(obs)/k(act)) at glass transition temperature (T(g)) was estimated to be approximately 0.6 and 0.8 at 6% RH and 12% RH, respectively, indicating that the degradation rate is significantly affected by molecular mobility at lower humidity conditions. However, these k(obs)/k(act) values at T(g) were larger than those for the insulin-trehalose system, and changes in the temperature-dependent slope around T(g) were less obvious than those for the insulin-trehalose system. Thus, the contribution of molecular mobility to the degradation rate in the insulin-PHEA system appeared to be less intense than that in the insulin-trehalose system. The subtle change in the temperature-dependent slope around T(g) observed in the insulin-PHEA system brought about a significant bias in shelf-life estimation when the reaction rate was extrapolated from temperatures above T(g) according to the Arrhenius equation. (c) 2006 Wiley-Liss, Inc. and the American Pharmacists Association

Extracellular Zinc Ion Inhibits ClC-0 Chloride Channels by Facilitating Slow Gating

PubMed Central

Chen, Tsung-Yu

1998-01-01

Extracellular Zn2+ was found to reversibly inhibit the ClC-0 Cl− channel. The apparent on and off rates of the inhibition were highly temperature sensitive, suggesting an effect of Zn2+ on the slow gating (or inactivation) of ClC-0. In the absence of Zn2+, the rate of the slow-gating relaxation increased with temperature, with a Q10 of ∼37. Extracellular Zn2+ facilitated the slow-gating process at all temperatures, but the Q10 did not change. Further analysis of the rate constants of the slow-gating process indicates that the effect of Zn2+ is mostly on the forward rate (the rate of inactivation) rather than the backward rate (the rate of recovery from inactivation) of the slow gating. When ClC-0 is bound with Zn2+, the equilibrium constant of the slow-gating process is increased by ∼30-fold, reflecting a 30-fold higher Zn2+ affinity in the inactivated channel than in the open-state channel. As examined through a wide range of membrane potentials, Zn2+ inhibits the opening of the slow gate with equal potency at all voltages, suggesting that a two-state model is inadequate to describe the slow-gating transition. Following a model originally proposed by Pusch and co-workers (Pusch, M., U. Ludewig, and T.J. Jentsch. 1997. J. Gen. Physiol. 109:105–116), the effect of Zn2+ on the activation curve of the slow gate can be well described by adding two constraints: (a) the dissociation constant for Zn2+ binding to the open channel is 30 μM, and (b) the difference in entropy between the open state and the transition state of the slow-gating process is increased by 27 J/ mol/°K for the Zn2+-bound channel. These results together indicate that extracellular Zn2+ inhibits ClC-0 by facilitating the slow-gating process. PMID:9834141

A benchtop biorobotic platform for in vitro observation of muscle-tendon dynamics with parallel mechanical assistance from an elastic exoskeleton.

PubMed

Robertson, Benjamin D; Vadakkeveedu, Siddarth; Sawicki, Gregory S

2017-05-24

We present a novel biorobotic framework comprised of a biological muscle-tendon unit (MTU) mechanically coupled to a feedback controlled robotic environment simulation that mimics in vivo inertial/gravitational loading and mechanical assistance from a parallel elastic exoskeleton. Using this system, we applied select combinations of biological muscle activation (modulated with rate-coded direct neural stimulation) and parallel elastic assistance (applied via closed-loop mechanical environment simulation) hypothesized to mimic human behavior based on previously published modeling studies. These conditions resulted in constant system-level force-length dynamics (i.e., stiffness), reduced biological loads, increased muscle excursion, and constant muscle average positive power output-all consistent with laboratory experiments on intact humans during exoskeleton assisted hopping. Mechanical assistance led to reduced estimated metabolic cost and MTU apparent efficiency, but increased apparent efficiency for the MTU+Exo system as a whole. Findings from this study suggest that the increased natural resonant frequency of the artificially stiffened MTU+Exo system, along with invariant movement frequencies, may underlie observed limits on the benefits of exoskeleton assistance. Our novel approach demonstrates that it is possible to capture the salient features of human locomotion with exoskeleton assistance in an isolated muscle-tendon preparation, and introduces a powerful new tool for detailed, direct examination of how assistive devices affect muscle-level neuromechanics and energetics. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effects of para-substituents of styrene derivatives on their chemical reactivity on platinum nanoparticle surfaces.

PubMed

Hu, Peiguang; Chen, Limei; Deming, Christopher P; Lu, Jia-En; Bonny, Lewis W; Chen, Shaowei

2016-06-09

Stable platinum nanoparticles were successfully prepared by the self-assembly of para-substituted styrene derivatives onto the platinum surfaces as a result of platinum-catalyzed dehydrogenation and transformation of the vinyl groups to the acetylene ones, forming platinum-vinylidene/-acetylide interfacial bonds. Transmission electron microscopic measurements showed that the nanoparticles were well dispersed without apparent aggregation, suggesting sufficient protection of the nanoparticles by the organic capping ligands, and the average core diameter was estimated to be 2.0 ± 0.3 nm, 1.3 ± 0.2 nm, and 1.1 ± 0.2 nm for the nanoparticles capped with 4-tert-butylstyrene, 4-methoxystyrene, and 4-(trifluoromethyl)styrene, respectively, as a result of the decreasing rate of dehydrogenation with the increasing Taft (polar) constant of the para-substituents. Importantly, the resulting nanoparticles exhibited unique photoluminescence, where an increase of the Hammett constant of the para-substituents corresponded to a blue-shift of the photoluminescence emission, suggesting an enlargement of the HOMO-LUMO band gap of the nanoparticle-bound acetylene moieties. Furthermore, the resulting nanoparticles exhibited apparent electrocatalytic activity towards oxygen reduction in acidic media, with the best performance among the series of samples observed with the 4-tert-butylstyrene-capped nanoparticles due to an optimal combination of the nanoparticle core size and ligand effects on the bonding interactions between platinum and oxygen species.

Failure of ESI Spectra to Represent Metal-Complex Solution Composition: A Study of Lanthanide-Carboxylate Complexes

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

McDonald, Luther W.; Campbell, James A.; Clark, Sue B.

2014-01-21

Electrospray ionization - mass spectrometry (ESI-MS) was used for the characterization of uranyl complexed to tributyl phosphate (TBP) and dibutyl phosphate (DBP). The stoichiometry of uranyl with TBP and DBP was determined, and the gas phase speciation was found to be dependent on the cone voltage applied to induce fragmentation on the gas phase complexes. To quantitatively compare the gas phase distribution of species to solution, apparent stability constants were calculated. With a cone voltage of 80V, the apparent stability constants for the complexes UO2(NO3)2•2TBP, UO2(NO3)2(H2O)•2TBP, and UO2(DBP)+ were determined. With a lower cone voltage applied, larger complexes were observedmore » and stability constants for the complexes UO2(NO3)2•3TBP and UO2(DBP)42- were determined.« less

Facilitated and selective oxidation of thiophenic sulfur compounds using MoOx/Al₂O₃-H₂O₂ system under ultrasonic irradiation.

PubMed

Akbari, Azam; Omidkhah, Mohammadreza; Towfighi Darian, Jafar

2015-03-01

Oxidative desulfurization of thiophenic sulfur compounds of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT) with MoOx/Al₂O₃ catalyst and H₂O₂ oxidant has been facilitated and more selective under ultrasonic irradiation. The catalyst with the optimum 10% of Mo loading consisted of isolated tetrahedral molybdenum oxide species based on FTIR analysis. The increase of Mo loading to 15% and 20% caused to generation of polymolybdate and MoO₃ crystals which decreased desulfurization activity. Sonication enhanced the apparent reaction rate constants in oxidation of all three sulfur compounds. An increase in the Arrhenius factor (A0), which is the total number of collisions per second, could explain the acceleration in the rate constants by sonication. The apparent activated energy (Ea) of BT oxidation was reduced from 96.6 to 75.3 kJ/mol by using ultrasound. This indicated that ultrasound had also a chemical effect, like a catalytic influence, in the acceleration of BT removal. DBT oxidation was reduced when investigated in the presence of tetralin, naphthalene and 2-methyl naphthalene as the model aromatic compounds of actual light oils. A higher selectivity toward DBT elimination in the presence of aromatics was obtained by sonication when compared with the silent treatment. Ultrasound cleaned the catalyst surface from adsorbed aromatics. On the basis of the obtained results, a mechanistic proposal for this desulfurization was explained. Oxidation was performed by nucleophilic attack of sulfur atom to the molybdenum peroxide species of tetrahedral molybdates, which was more advanced by sonication. Copyright © 2014 Elsevier B.V. All rights reserved.

Photoinduced Reactions of Benzophenone in Biaxially Oriented Polypropylene.

PubMed

Levin, Peter P; Efremkin, Alexei F; Krivandin, Aleksey V; Lomakin, Sergei M; Shatalova, Olga V; Khudyakov, Igor V

2018-05-03

The photoinduced reactions of benzophenone (B) in biaxially oriented polypropylene (BOPP) were studied with nanosecond laser photolysis (N 2 laser, λ337.1 nm). The first observed transient was a triplet state 3 B*. Decay of 3 B* led to formation of a radical pair (RP) of BH • and R • , where R • is a radical formed by hydrogen abstraction from BOPP (RH) by 3 B*. We studied BOPP after the preheating for a short time in a temperature range 298-423 K, which is essentially lower than its melting point of 453 K. All measurements with not-heated and with preheated (annealed) BOPP were made at 298 K. A radical pair (RP) apparently decays as a contact pair 3 [BH • , R • ] in nonheated BOPP. A critical phenomenon takes place: dissociation of RP with a formation of free radicals in the polymer bulk is observed at preheating temperature T crit ≈ 403 K and at a higher T. The physical process of heating and cooling of BOPP apparently resulted in the restructuring of crystallites, their agglomeration, shrinking of the distribution of crystallites according to their sizes in BOPP. Overall BOPP becomes softer which manifests itself in the radical kinetics. The decay kinetics of 3 B* and RP in the cage fits well the first-order law. Rate constants were obtained. Radicals BH • , which exit into the polymer bulk at temperatures of preheating T ≥ 403 K, decay by cross-termination according to the second-order law. A relatively high rate constant ∼10 8 M -1 ·s -1 for this reaction was obtained due to diffusion of BH • enclosed in the soft amorphous phase of BOPP. Properties of BOPP containing B were studied with ESR, DSC, IR, and WAXD.

Kinetics of surface processes for Mo(CO){sub 6} on partially dehydroxylated alumina and hydroxylated alumina. Observation of Mo(CO){sub 5}(ads)

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

Reddy, K.P.; Brown, T.L.

1995-03-15

The adsorption of Mo(CO){sub 6} on partially dehydroxylated alumina (PDA) and hydroxylated alumina (HA) has been studied using IR and UV-vis spectroscopy. The results from these experiments suggest that the initially physisorbed Mo(CO){sub 6} coordinates to two distinct Lewis acid sites on the surface of PDA, one much more abundant than the other, with an apparent single rate constant 2.3 x 10{sup {minus}3} s{sup {minus}1} at 298 K. The Mo(CO){sub 6}(ads) in turn loses CO reversibly, with an apparent single rate constant 1.8 x 10{sup {minus}4} s{sup {minus}1} at 298 K to form Mo(CO){sub 5}(ads). Upon removal of gas phasemore » CO released in the first step, Mo(CO){sub 5}(ads) loses two additional COs to form Mo(CO){sub 3}(ads). Alternatively, on HA physisorbed Mo(CO){sub 6} undergoes nucleophilic attack by hydroxyl groups, which results in cis-labilization of a carbonyl group, leading in turn to the formation of Mo(CO){sub 5}(L), where L is a surface hydroxyl. The Mo(CO){sub 5}(L) so formed loses additional carbonyls to form a lower subcarbonyl. The decarbonylation process appears to be faster than on PDA. The experimental data indicate that there are no Al{sup 31} exposed on HA. All the observed decarbonylation processes are reversible under CO at room temperature on both HA and PDA. The addition of CO{sub 2} to the subcarbonyl on HA results in the formation of a bicarbonate, with displacement of the subcarbonyls. 24 refs., 11 figs., 1 tab.« less

Population Pharmacokinetics of Oral Topotecan in Infants and Very Young Children with Brain Tumors Demonstrates a Role of ABCG2 rs4148157 on the Absorption Rate Constant

PubMed Central

Roberts, Jessica K.; Birg, Anna V.; Lin, Tong; Daryani, Vinay M.; Panetta, John C.; Broniscer, Alberto; Robinson, Giles W.; Gajjar, Amar J.

2016-01-01

For infants and very young children with brain tumors, chemotherapy after surgical resection is the main treatment due to neurologic and neuroendocrine adverse effects from whole brain irradiation. Topotecan, an anticancer drug with antitumor activity against pediatric brain tumors, can be given intravenous or orally. However, high interpatient variability in oral drug bioavailability is common in children less than 3 years old. Therefore, this study aimed to determine the population pharmacokinetics of oral topotecan in infants and very young children, specifically evaluating the effects of age and ABCG2 and ABCB1 on the absorption rate constant (Ka), as well as other covariate effects on all pharmacokinetic parameters. A nonlinear mixed effects model was implemented in Monolix 4.3.2 (Lixoft, Orsay, France). A one-compartment model with first-order input and first-order elimination was found to adequately characterize topotecan lactone concentrations with population estimates as [mean (S.E.)]; Ka = 0.61 (0.11) h−1, apparent volume of distribution (V/F) = 40.2 (7.0) l, and apparent clearance (CL/F) = 40.0 (2.9) l/h. After including the body surface area in the V/F and CL/F as a power model centered on the population median, the ABCG2 rs4148157 allele was found to play a significant role in the value of Ka. Patients homozygous or heterozygous for G>A demonstrated a Ka value 2-fold higher than their GG counterparts, complemented with a 2-fold higher maximal concentration as well. These results demonstrate a possible role for the ABCG2 rs4148157 allele in the pharmacokinetics of oral topotecan in infants and very young children, and warrants further investigation. PMID:27052877

pH dependence of cyanide binding to the ferric heme domain of the direct oxygen sensor from Escherichia coli and the effect of alkaline denaturation.

PubMed

Bidwai, Anil K; Ok, Esther Y; Erman, James E

2008-09-30

The spectrum of the ferric heme domain of the direct oxygen sensor protein from Escherichia coli ( EcDosH) has been measured between pH 3.0 and 12.6. EcDosH undergoes acid denaturation with an apparent p K a of 4.24 +/- 0.05 and a Hill coefficient of 3.1 +/- 0.6 and reversible alkaline denaturation with a p K a of 9.86 +/- 0.04 and a Hill coefficient of 1.1 +/- 0.1. Cyanide binding to EcDosH has been investigated between pH 4 and 11. The EcDosH-cyanide complex is most stable at pH 9 with a K D of 0.29 +/- 0.06 microM. The kinetics of cyanide binding are monophasic between pH 4 and 8. At pH >or=8.5, the reaction is biphasic with the fast phase dependent upon the cyanide concentration and the slow phase independent of cyanide. The slow phase is attributed to conversion of denatured EcDosH to the native state, with a pH-independent rate of 0.052 +/- 0.006 s (-1). The apparent association rate constant for cyanide binding to EcDosH increases from 3.6 +/- 0.1 M (-1) s (-1) at pH 4 to 520 +/- 20 M (-1) s (-1) at pH 11. The dissociation rate constant averages (8.6 +/- 1.3) x 10 (-5) s (-1) between pH 5 and 9, increasing to (1.4 +/- 0.1) x 10 (-3) s (-1) at pH 4 and (2.5 +/- 0.1) x 10 (-3) s (-1) at pH 12.2. The mechanism of cyanide binding is consistent with preferential binding of the cyanide anion to native EcDosH. The reactions of imidazole and H 2O 2 with ferric EcDosH were also investigated and show little reactivity.

Progress Report on FY15 Crystalline Experiments M4FT-15LL0807052

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

Zavarin, M.; Zhao, P.; Joseph, C.

2015-08-13

Colloid-facilitated plutonium transport is expected to be the dominant mechanism in its migration through the environment. The forms of Pu colloids (intrinsic versus pseudo-colloid) and their stabilities control temporal and spatial scales of Pu transport in the environment. In the present study, we examine the stability of Pu intrinsic colloids freshly prepared in alkaline solution relative to Pu-montmorillonite pseudo-colloids using a dialysis device and modeling approaches. Intrinsic colloids prepared under alkaline conditions were found to be unstable over a timescale of months. The kinetics of multiple processes, including hydrolysis/precipitation of Pu(IV), dissolution of intrinsic colloids in the absence and presencemore » of the clay colloids, transport of dissolved Pu species across the dialysis membrane, and formation of pseudo-colloids were examined. The dissolution of intrinsic colloids was the rate-limiting process in most cases. The apparent intrinsic colloid dissolution rate constants range from 6×10 -7 to 1×10 - 6 mol·m -2·day -1 and 4×10 -6 to 8×10 -6 mol·m -2·day -1 at 25 and 80°C, respectively, while the apparent diffusion rate constants for Pu ions crossing the dialysis membrane are >200 times higher. Elevated temperatures enhance dissolution of Pu colloids and the activation energy for the process is estimated to be 28 kJ mol -1. The sorption of Pu to montmorillonite appears to be endothermic as the affinity of Pu for the clay increases with increasing temperature. Our results provide an in-depth understanding of how intrinsic and pseudo-colloids interact with each other kinetically. Although the fact that intrinsic colloids tend to dissolve in the presence of montmorillonite and transform into pseudo-colloids may limit the migration of intrinsic colloids, the thermodynamically more stable pseudo-colloids may play an important role in Pu transport in the environment over significant temporal and spatial scales.« less

High-Affinity Binding of Remyelinating Natural Autoantibodies to Myelin-Mimicking Lipid Bilayers Revealed by Nanohole Surface Plasmon Resonance

PubMed Central

Wittenberg, Nathan J.; Im, Hyungsoon; Xu, Xiaohua; Wootla, Bharath; Watzlawik, Jens; Warrington, Arthur E.; Rodriguez, Moses; Oh, Sang-Hyun

2012-01-01

Multiple sclerosis is a progressive neurological disorder that results in the degradation of myelin sheaths that insulate axons in the central nervous system. Therefore promotion of myelin repair is a major thrust of multiple sclerosis treatment research. Two mouse monoclonal natural autoantibodies, O1 and O4, promote myelin repair in several mouse models of multiple sclerosis. Natural autoantibodies are generally polyreactive and predominantly of the IgM isotype. The prevailing paradigm is that because they are polyreactive, these antibodies bind antigens with low affinities. Despite their wide use in neuroscience and glial cell research, however, the affinities and kinetic constants of O1 and O4 antibodies have not been measured to date. In this work, we developed a membrane biosensing platform based on surface plasmon resonance in gold nanohole arrays with a series of surface modification techniques to form myelin-mimicking lipid bilayer membranes to measure both the association and dissociation rate constants for O1 and O4 antibodies binding to their myelin lipid antigens. The ratio of rate constants shows that O1 and O4 bind to galactocerebroside and sulfated galactocerebroside, respectively, with unusually small apparent dissociation constants (KD ~0.9 nM) for natural autoantibodies. This is approximately one to two orders of magnitude lower than typically observed for the highest affinity natural autoantibodies. We propose that the unusually high affinity of O1 and O4 to their targets in myelin contributes to the mechanism by which they signal oligodendrocytes and induce central nervous system repair. PMID:22762372

Population pharmacokinetics of telapristone (CDB-4124) and its active monodemethylated metabolite CDB-4453, with a mixture model for total clearance.

PubMed

Morris, Denise; Podolski, Joseph; Kirsch, Alan; Wiehle, Ronald; Fleckenstein, Lawrence

2011-12-01

Telapristone is a selective progesterone antagonist that is being developed for the long-term treatment of symptoms associated with endometriosis and uterine fibroids. The population pharmacokinetics of telapristone (CDB-4124) and CDB-4453 was investigated using nonlinear mixed-effects modeling. Data from two clinical studies (n = 32) were included in the analysis. A two-compartment (parent) one compartment (metabolite) mixture model (with two populations for apparent clearance) with first-order absorption and elimination adequately described the pharmacokinetics of telapristone and CDB-4453. Telapristone was rapidly absorbed with an absorption rate constant (Ka) of 1.26 h(-1). Moderate renal impairment resulted in a 74% decrease in Ka. The population estimates for oral clearance (CL/F) for the two populations were 11.6 and 3.34 L/h, respectively, with 25% of the subjects being allocated to the high-clearance group. Apparent volume of distribution for the central compartment (V2/F) was 37.4 L, apparent inter-compartmental clearance (Q/F) was 21.9 L/h, and apparent peripheral volume of distribution for the parent (V4/F) was 120 L. The ratio of the fraction of telapristone converted to CDB-4453 to the distribution volume of CDB-4453 (Fmet(est)) was 0.20/L. Apparent volume of distribution of the metabolite compartment (V3/F) was fixed to 1 L and apparent clearance of the metabolite (CLM/F) was 2.43 L/h. A two-compartment parent-metabolite model adequately described the pharmacokinetics of telapristone and CDB-4453. The clearance of telapristone was separated into two populations and could be the result of metabolism via polymorphic CYP3A5.

Yeast hexokinase. A fluorescence temperature-jump study of the kinetics of the binding of glucose to the monomer forms of hexokinases P-I and P-II.

PubMed

Hoggett, J G; Kellett, G L

1976-09-15

The binding of glucose to the monomeric forms of hexokinases P-I and P-II in Tris and phosphate buffers at pH 8.0 in the presence of 1 mol l-1 KCl has been studied using the fluorescence temperature-jump technique. For both isozymes only one relaxation time was observed; values of tau-1 increased linearly with increasing concentration of free reacting partners. The apparent second-order rate constant for association was about 2 X 10(6) 1 mol-1 s-1 for both isozymes; the differences in the stabilities of the complexes with P-I and P-II are entirely attributable to the fact that glucose dissociates more slowly from its complex with P-I than P-II (approximately 300 s-1 and 1100 s-1 respectively). Although the kinetic data are compatible with a single-step mechanism for glucose binding the association rate constant was much lower than that expected for a diffusion-limited rate of encounter. Other mechanisms for describing an induced-fit are discussed. It is shown that the data are incompatible with a slow 'prior-isomerization' pathway of substrate binding, but are consistent with a 'substrate-guided' pathway involving isomerization of the enzyme-substrate complex.

Radioimmunoassay for pyridostigmine

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

Meyer, H.G.; Lukey, B.J.; Gepp, R.T.

1988-01-01

Pyridostigmine is a cholinergic drug used for the treatment of myasthenia gravis and for antagonizing the effects of non-depolarizing muscle relaxants. In addition, military organizations in several countries have an active interest in pyridostigmine as a pretreatment compound for nerve agent poisoning. Anti-pyridostigmine antibodies were produced in rabbits using a pyridostigmine analog conjugated to keyhole limpet hemocyanin. These antibodies were used for development of a radioimmunoassay that has a linear standard curve (r2=0.986) ranging from 0.5 to 10.0 ng/ml of pyridostigmine bromide in a 0.1-ml plasma sample. This assay measures pyridostigmine in plasma with better sensitivity and much greater through-putmore » than do current state-of-the-art high-performance liquid chromatography techniques. In addition, only small volumes (100ml) of the plasma samples are required. Plasma levels of pyridostigmine were determined in the rat after intramuscular administration (0.056mg/kg) of pyridostigmine bromide. Estimates of the various pharmacokinetic parameters were calculated using the computer program NONLIN84. The results were as follows: apparent volume of distribution = 1.97 1/kg, absorption rate constant = 0.277 min-1, elimination rate constant = 0.0273 min-1, area under the curve = 1010 ng x min/ml, absorption rate half-life = 2.41 min, elimination rate half-life = 24.8 min, maximal plasma concentration (Cmax) = 21.3 ng/ml and time to Cmax = 9.02 min.« less

Modeling As(III) oxidation and removal with iron electrocoagulation in groundwater.

PubMed

Li, Lei; van Genuchten, Case M; Addy, Susan E A; Yao, Juanjuan; Gao, Naiyun; Gadgil, Ashok J

2012-11-06

Understanding the chemical kinetics of arsenic during electrocoagulation (EC) treatment is essential for a deeper understanding of arsenic removal using EC under a variety of operating conditions and solution compositions. We describe a highly constrained, simple chemical dynamic model of As(III) oxidation and As(III,V), Si, and P sorption for the EC system using model parameters extracted from some of our experimental results and previous studies. Our model predictions agree well with both data extracted from previous studies and our observed experimental data over a broad range of operating conditions (charge dosage rate) and solution chemistry (pH, co-occurring ions) without free model parameters. Our model provides insights into why higher pH and lower charge dosage rate (Coulombs/L/min) facilitate As(III) removal by EC and sheds light on the debate in the recent published literature regarding the mechanism of As(III) oxidation during EC. Our model also provides practically useful estimates of the minimum amount of iron required to remove 500 μg/L As(III) to <50 μg/L. Parameters measured in this work include the ratio of rate constants for Fe(II) and As(III) reactions with Fe(IV) in synthetic groundwater (k(1)/k(2) = 1.07) and the apparent rate constant of Fe(II) oxidation with dissolved oxygen at pH 7 (k(app) = 10(0.22) M(-1)s(-1)).

Impact of cool versus warm temperatures on gestation in the aspic viper (Vipera aspis).

PubMed

Michel, Catherine Louise; Pastore, Jean-Henri; Bonnet, Xavier

2013-07-01

Previous experimental data suggested that digestion and growth rates are not impaired under cool constant temperature (23°C) in a viviparous snake (Vipera aspis). These results challenged the widespread notion that both elevated temperatures (e.g. 30°C) and temperature fluctuations are required for digestion and growth in temperate climate reptiles. Here, we investigated the impact of constant cool temperatures on another physiological performance that is crucial to population persistence: gestation. At the time when reproductive females were midway through vitellogenesis, we placed ten reproductive and two non-reproductive female aspic vipers at each of two contrasted constant temperature conditions: cool (23°C) versus warm (28°C). Sixty percent of the females placed at 28°C gave birth to healthy offspring, suggesting that constant warm body temperatures were compatible with normal offspring production. Conversely, none of the cool females gave birth to healthy offspring. A blister disease affected exclusively cool pregnant females. Apparently, the combination of cool temperatures plus gestation was too challenging for such females. Our results suggest that reproduction is more thermally sensitive than digestion or growth, indeed gestation faltered under moderately cool thermal constraints. This sensitivity could be a crucial factor determining the capacity of this species to colonize different habitats. Copyright © 2013 Elsevier Inc. All rights reserved.

Henry’s Law Constant and Overall Mass Transfer Coefficient for Formaldehyde Emission from Small Water Pools under Simulated Indoor Environmental Conditions

EPA Science Inventory

The Henry’s law constant (HLC) and the overall mass transfer coefficient are both important parameters for modeling formaldehyde emissions from aqueous solutions. In this work, the apparent HLCs for aqueous formaldehyde solutions were determined in the concentration range from 0....

Radiocarbon dating of open systems with bomb effect

NASA Technical Reports Server (NTRS)

Mckay, C. P.; Long, A.; Friedmann, E. I.

1986-01-01

The application of radiocarbon dating is extended to include systems that are slowly exchanging carbon with the atmosphere. Simple formulae are derived that relate the true age and the exchange rate of carbon to the apparent radiocarbon age. A radiocarbon age determination does not give a unique true age and exchange rate but determines a locus of values bounded by a minimum age and a minimum exchange rate. It is found that for radiocarbon ages as large as 10,000 years it is necessary to correct for the anthropogenic radiocarbon produced in the atmosphere by nuclear weapons testing. A one-term exponential approximation, with an e-folding time of 14.43 years, is used to model this effect and is shown to be accurate to within 3 percent for exchange time constants of 100 years and greater. The approach developed here is not specific to radiocarbon and can be applied to other radioisotopes in open systems.

Body size development of captive and free-ranging Leopard tortoises (Geochelone pardalis).

PubMed

Ritz, Julia; Hammer, Catrin; Clauss, Marcus

2010-01-01

The growth and weight development of Leopard tortoise hatchings (Geochelone pardalis) kept at the Al Wabra Wildlife Preservation (AWWP), Qatar, was observed for more than four years, and compared to data in literature for free-ranging animals on body weight or carapace measurements. The results document a distinctively faster growth in the captive animals. Indications for the same phenomenon in other tortoise species (Galapagos giant tortoises, G. nigra; Spur-thighed tortoises, Testudo graeca; Desert tortoises, Gopherus agassizi) were found in the literature. The cause of the high growth rate most likely is the constant provision with highly digestible food of low fiber content. Increased growth rates are suspected to have negative consequences such as obesity, high mortality, gastrointestinal illnesses, renal diseases, "pyramiding," fibrous osteodystrophy or metabolic bone disease. The apparently widespread occurrence of high growth rates in intensively managed tortoises underlines how easily ectothermic animals can be oversupplemented with nutrients. (c) 2009 Wiley-Liss, Inc.

Removal of halogenated emerging contaminants from water by nitrogen-doped graphene decorated with palladium nanoparticles: Experimental investigation and theoretical analysis.

PubMed

Li, Lei; Gong, Li; Wang, Yi-Xuan; Liu, Qi; Zhang, Jie; Mu, Yang; Yu, Han-Qing

2016-07-01

The removal performance and mechanisms of halogenated emerging contaminants from water by palladium decorated nitrogen-doped graphene (Pd/NG) were investigated in this study. For comparison, three catalysts of Pd/NG, palladium decorated graphene (Pd/G) and commercial Pd/C were initially explored to degrade tetrabromobisphenol A (TBBPA). After that, the influence of various environmental parameters on TBBPA removal by the Pd/NG catalyst was evaluated. Moreover, both Langmuir-Hinshelwood model and density functional theory (DFT) were adopted to theoretically elucidate the adsorption and the activation of TBBPA on the catalyst. The results show that the apparent rate constant of TBBPA dehalogenation was increased by 26.7% and 39.0% in the presence of the Pd/NG catalyst compared to the Pd/G and Pd/C ones. Higher temperature, catalyst dosage and alkaline conditions resulted in the enhancement of TBBPA dehalogenation by the Pd/NG catalyst, while humic acid in the solution had a negatively effect on the transformation of TBBPA. The corresponding rate constant value exhibited a 2.1- and 1.8-fold increase with the rise of temperature from 298 to 328 K and initial pH from 6.5 to 9.0, respectively. On the contrary, the rate constant was decreased by 78.9% in the presence of 15 mg L(-1) humic acid. Theoretical analysis revealed that both adsorption and activation processes of TBBPA on the Pd/NG catalyst were enhanced through the N doping into graphene framework. Copyright © 2016 Elsevier Ltd. All rights reserved.

A highly efficient nano-cluster artificial peroxidase and its direct electrochemistry on a nano complex modified glassy carbon electrode.

PubMed

Hong, Jun; Wang, Wei; Huang, Kun; Yang, Wei-Yun; Zhao, Ying-Xue; Xiao, Bao-Lin; Gao, Yun-Fei; Moosavi-Movahedi, Zainab; Ghourchian, Hedayatollah; Moosavi-Movahedi, Ali Akbar

2012-01-01

A nano-cluster with highly efficient peroxide activity was constructed based on nafion (NF) and cytochrome c (Cyt c). UV-Vis spectrometry and transmission electron microscopy (TEM) methods were utilized for characterization of the nano-structured enzyme or artificial peroxidase (AP). The nano-cluster was composed of a Chain-Ball structure, with an average ball size of about 40 nm. The Michaelis-Menten (K(m)) and catalytic rate (k(cat)) constants of the AP were determined to be 2.5 ± 0.4 µM and 0.069 ± 0.001 s(-1), respectively, in 50 mM PBS at pH 7.0. The catalytic efficiency of the AP was evaluated to be 0.028 ± 0.005 µM(-1) s(-1), which was 39 ± 5% as efficient as the native horseradish peroxidase (HRP). The AP was also immobilized on a functional multi-wall carbon nanotube (MWNCTs)-gold colloid nanoparticles (AuNPs) nano-complex modified glassy carbon (GC) electrode. The cyclic voltammetry of AP on the nano complex modified GC electrode showed a pair of well-defined redox peaks with a formal potential (E°') of -45 ± 2 mV (vs. Ag/AgCl) at a scan rate of 0.05 V/s. The heterogeneous electron transfer rate constant (k(s)) was evaluated to be 0.65 s(-1). The surface concentration of electroactive AP on GC electrode (Γ) was 7 × 10(-10) mol cm(-2). The apparent Michaelis-Menten constant (K(m)(app)) was 0.23 nM.

Kinetics and mass-transfer phenomena in anaerobic granular sludge.

PubMed

Gonzalez-Gil, G; Seghezzo, L; Lettinga, G; Kleerebezem, R

2001-04-20

The kinetic properties of acetate-degrading methanogenic granular sludge of different mean diameters were assessed at different up-flow velocities (V(up)). Using this approach, the influence of internal and external mass transfer could be estimated. First, the apparent Monod constant (K(S)) for each data set was calculated by means of a curve-fitting procedure. The experimental results revealed that variations in the V(up) did not affect the apparent K(S)-value, indicating that external mass-transport resistance normally can be neglected. With regard to the granule size, a clear increase in K(S) was found at increasing granule diameters. The experimental data were further used to validate a dynamic mathematical biofilm model. The biofilm model was able to describe reaction-diffusion kinetics in anaerobic granules, using a single value for the effective diffusion coefficient in the granules. This suggests that biogas formation did not influence the diffusion-rates in the granular biomass. Copyright 2001 John Wiley & Sons, Inc.

Integrated Population Pharmacokinetic Analysis of Rivaroxaban Across Multiple Patient Populations

PubMed Central

Zhang, Liping; Frede, Matthias; Kubitza, Dagmar; Mueck, Wolfgang; Schmidt, Stephan; Solms, Alexander; Yan, Xiaoyu; Garmann, Dirk

2018-01-01

The population pharmacokinetics (PK) of rivaroxaban have been evaluated in several population‐specific models. We developed an integrated population PK model using pooled data from 4,918 patients in 7 clinical trials across all approved indications. Effects of gender, age, and weight on apparent clearance (CL/F) and apparent volume of distribution (V/F), renal function, and comedication on CL/F, and relative bioavailability as a function of dose (F) were analyzed. Virtual subpopulations for exposure simulations were defined by age, creatinine clearance (CrCL) and body mass index (BMI). Rivaroxaban PK were adequately described by a one‐compartment disposition model with a first‐order absorption rate constant. Significant effects of CrCL, use of comedications, and study population on CL/F, age, weight, and gender on V/F, and dose on F were identified. CrCL had a modest influence on exposure, whereas age and BMI had a minor influence. The model was suitable to predict rivaroxaban exposure in patient subgroups of special interest. PMID:29660785

Synthesis and characterization of rod like C doped ZnO nanoparticles with enhanced photocatalytic activities

NASA Astrophysics Data System (ADS)

Labhane, P. K.; Sapkal, B. M.; Sonawane, G. H.

2018-05-01

Carbon (C) doped ZnO rod like nanoparticles were prepared by simple co-precipitation method. The effect of C doping on ZnO has been evaluated by using XRD, Williamson-Hall Plot, FESEM and EDX data. UV light assisted photocatalytic activities of prepared samples were evaluated spectrophotometrically by the degradation of methylene blue (MB). C doped ZnO shows excellent catalytic efficiency compared to pure ZnO, degrading MB completely within 100 min under UV light. Photocatalysis follows the first order kinetics law and the calculated apparent reaction kinetics rate constant suggest the better activity of C-ZnO.

Oxygen reactivity of the biferrous site in the de novo designed four helix bundle peptide DFsc: nature of the "intermediate" and reaction mechanism.

PubMed

Calhoun, Jennifer R; Bell, Caleb B; Smith, Thomas J; Thamann, Thomas J; DeGrado, William F; Solomon, Edward I

2008-07-23

The DFsc and DFscE11D de novo designed protein scaffolds support biomimetic diiron cofactor sites that react with dioxygen forming a 520 nm "intermediate" species with an apparent pseudo-first-order formation rate constant of 2.2 and 4.8 s-1, respectively. Resonance Raman spectroscopy shows that this absorption feature is due to a phenolate-to-ferric charge transfer transition arising from a single tyrosine residue coordinating terminally to one of the ferric ions in the site. Phenol coordination could provide a proton to promote rapid loss of a putative peroxo species.

Characterization of Actinides Complexed to Nuclear Fuel Constituents Using ESI-MS.

PubMed

McDonald, Luther W; Campbell, James A; Vercouter, Thomas; Clark, Sue B

2016-03-01

Electrospray ionization-mass spectrometry (ESI-MS) was tested for its use in monitoring spent nuclear fuel (SNF) constituents including U, Pu, dibutyl phosphate (DBP), and tributyl phosphate (TBP). Both positive and negative ion modes were used to evaluate the speciation of U and Pu with TBP and DBP. Furthermore, apparent stability constants were determined for U complexed to TBP and DBP. In positive ion mode, TBP produced a strong signal with and without complexation to U or Pu, but, in negative ion mode, no TBP, U-TBP, or Pu-TBP complexes were observed. Apparent stability constants were determined for [UO2(NO3)2(TBP)2], [UO2(NO3)2(H2O)(TBP)2], and [UO2(NO3)2(TBP)3]. In contrast DBP, U-DBP, and Pu-DBP complexes were observed in both positive and negative ion modes. Apparent stability constants were determined for the species [UO2(DBP)], [UO2(DBP)3], and [UO2(DBP)4]. Analyzing mixtures of U or Pu with TBP and DBP yielded the formation of ternary complexes whose stoichiometry was directly related to the ratio of TBP to DBP. The ESI-MS protocols used in this study will further demonstrate the utility of ESI-MS and its applicability to process control monitoring in SNF reprocessing facilities.

Into the theory of the partial-filling affinity capillary electrophoresis and the determination of apparent stability constants of analyte-ligand complexes.

PubMed

Ansorge, Martin; Dubský, Pavel; Ušelová, Kateřina

2018-03-01

The partial-filling affinity capillary electrophoresis (pf-ACE) works with a ligand present in a background electrolyte that forms a weak complex with an analyte. In contrast to a more popular mobility-shift affinity capillary electrophoresis, only a short plug of the ligand is introduced into a capillary in the pf-ACE. Both methods can serve for determining apparent stability constants of the formed complexes but this task is hindered in the pf-ACE by the fact that the analyte spends only a part of its migration time in a contact with the ligand. In 1998, Amini and Westerlund published a linearization strategy that allows for extracting an effective mobility of an analyte in the presence of a neutral ligand out of the pf-ACE data. The main purpose of this paper is to show that the original formula is only approximate. We derive a new formula and demonstrate its applicability by means of computer simulations. We further inspect several strategies of data processing in the pf-ACE regarding a risk of an error propagation. This establishes a good practice of determining apparent stability constants of analyte-ligand complexes by means of the pf-ACE. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Assessment of potential for natural attenuation of chlorinated ethenes and ethanes in ground water at a petrochemical reclamation site, Harris County, Texas

USGS Publications Warehouse

Huff, Glenn F.; Braun, Christopher L.; Lee, Roger W.

2000-01-01

Redox conditions in the Numerous Sand Channels Zone beneath a petrochemical reclamation site in Harris County, Texas, range from sulfate reducing to methanogenic as indicated by the presence of methane in ground water and the range of molecular hydrogen concentrations. Assessment of the potential for reductive dechlorination using BIOCHLOR as a screening tool indicated conditions favoring anaerobic degradation of chlorinated organic compounds in the Numerous Sand Channels Zone. Evidence supporting reductive dechlorination includes apparently biogenic cis-1,2-dichloroethene; an increased ratio of 1,2-dichloroethane to 1,1,2-trichloroethane downgradient from the assumed contaminant source area; ethene and methane concentrations greater than background concentrations within the area of the contaminant plume; and a positive correlation of the ratio of ethene to vinyl chloride as a function of methane concentrations. The body of evidence presented in this report argues for hydrogenolysis of trichloroethene to cis-1,2-dichloroethene; of 1,1,2-trichloroethane to 1,2-dichloroethane; and of vinyl chloride to ethene within the Numerous Sand Channels Zone. Simulations using BIOCHLOR yielded apparent first-order decay constants for reductive dechlorination in the sequence Tetrachloroethene --> trichloroethene --> cis-1,2-dichloroethene --> vinyl chloride --> ethene within the range of literature values reported for each compound and apparent first-order decay constants for reductive dechlorination in the sequence 1,1,2-trichloroethane --> 1,2-dichloroethane slightly greater than literature values reported for each compound along the upgradient segment of a simulated ground-water flowpath. Except for vinyl chloride, apparent rates of reductive dechlorination for all simulated species show a marked decrease along the downgradient segment of the simulated ground-water flowpath. Evidence for reductive dechlorination of chlorinated ethenes within the Numerous Sand Channels Zone indicates potential for natural attenuation of chlorinated ethenes. Reductive dechlorination of chlorinated ethanes apparently occurs to a lesser extent, indicating relatively less potential for natural attenuation of chlorinated ethanes. Additional data are needed on the concentrations and distribution of chlorinated ethenes and ethanes in individual fine sand intervals of the Numerous Sand Channels Zone. This information, combined with lower minimum reporting levels for future chloroethane analyses, might enable a more complete and quantitative assessment of the potential for natural attenuation at the site.

High Pressure ZZ-Exchange NMR Reveals Key Features of Protein Folding Transition States.

PubMed

Zhang, Yi; Kitazawa, Soichiro; Peran, Ivan; Stenzoski, Natalie; McCallum, Scott A; Raleigh, Daniel P; Royer, Catherine A

2016-11-23

Understanding protein folding mechanisms and their sequence dependence requires the determination of residue-specific apparent kinetic rate constants for the folding and unfolding reactions. Conventional two-dimensional NMR, such as HSQC experiments, can provide residue-specific information for proteins. However, folding is generally too fast for such experiments. ZZ-exchange NMR spectroscopy allows determination of folding and unfolding rates on much faster time scales, yet even this regime is not fast enough for many protein folding reactions. The application of high hydrostatic pressure slows folding by orders of magnitude due to positive activation volumes for the folding reaction. We combined high pressure perturbation with ZZ-exchange spectroscopy on two autonomously folding protein domains derived from the ribosomal protein, L9. We obtained residue-specific apparent rates at 2500 bar for the N-terminal domain of L9 (NTL9), and rates at atmospheric pressure for a mutant of the C-terminal domain (CTL9) from pressure dependent ZZ-exchange measurements. Our results revealed that NTL9 folding is almost perfectly two-state, while small deviations from two-state behavior were observed for CTL9. Both domains exhibited large positive activation volumes for folding. The volumetric properties of these domains reveal that their transition states contain most of the internal solvent excluded voids that are found in the hydrophobic cores of the respective native states. These results demonstrate that by coupling it with high pressure, ZZ-exchange can be extended to investigate a large number of protein conformational transitions.

A comparative approach of methylparaben photocatalytic degradation assisted by UV-C, UV-A and Vis radiations.

PubMed

Doná, Giovanna; Dagostin, João Luiz Andreoti; Takashina, Thiago Atsushi; de Castilhos, Fernanda; Igarashi-Mafra, Luciana

2018-05-01

Due to the widespread use of methylparaben (MEP) and its high chemical stability, it can be found in wastewater treatment plants and can act as an endocrine disrupting compound. In this study, the photocatalytic degradation and mineralization of MEP solutions were evaluated under UV-A, UV-C and Vis radiations in the presence of the photocatalyst TiO 2 . In this sense, the effects of the catalyst load, pH and MEP initial concentration were studied. Remarkably higher reaction rates and total photodegradation were achieved in systems assisted by UV-C radiation. The complete degradation was achieved after 60 min of reaction using the MEP concentration of 30 mg L -1 at pH 9 and 500 mg L -1 TiO 2 . The experimental data apparently followed a Langmuir-Hinshelwood kinetic model, which could predict 88-98% of the reaction behavior. For the best photodegradation condition, the model predicted an apparent reaction rate constant (k app ) equal to 0.0505 min -1 and an initial reaction rate of 1.5641 mg (L min) -1 . Mineralization analyses showed high removal for MEP and derived compounds from the initial solution when using UV-C after 90 min of reaction. The lower toxicity was also confirmed by in vivo tests using MEP solutions previously treated by photocatalysis.

Excess zinc ions are a competitive inhibitor for carboxypeptidase A

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

Hirose, J.; Ando, S.; Kidani, Y.

The mechanism for inhibition of enzyme activity by excess zinc ions has been studied by kinetic and equilibrium dialysis methods at pH 8.2, I = 0.5 M. With carboxypeptidase A (bovine pancreas), peptide (carbobenzoxyglycyl-L-phenylalanine and hippuryl-L-phenylalanine) and ester (hippuryl-L-phenyl lactate) substrates were inhibited competitively by excess zinc ions. The K/sub i/ values for excess zinc ions with carboxypeptidase A at pH 8.2 are all similar. The apparent constant for dissociation of excess zinc ions from carboxypeptidase A was also obtained by equilibrium dialysis at pH 8.2 and was 2.4 x 10/sup -5/ M, very close to the K/sub i/ valuesmore » above. With arsanilazotyrosine-248 carboxypeptidase A ((Azo-CPD)Zn)), hippuryl-L-phenylalanine, carbobenzoxyglycyl-L-phenylalanine, and hippuryl-L-phenyl lactate were also inhibited with a competitive pattern by excess zinc ions, and the K/sub i/ values were (3.0-3.5) x 10/sup -5/ M. The apparent constant for dissociation of excess zinc ions from arsanilazotyrosine-248 carboxypeptidase A, which was obtained from absorption changes at 510 nm, was 3.2 x 10/sup -5/ M and is similar to the K/sub i/ values for ((Azo-CPD)Zn). The apparent dissociation and inhibition constants, which were obtained by inhibition of enzyme activity and spectrophotometric and equilibrium dialysis methods with native carboxypeptidase A and arsanilazotyrosine-248 carboxypeptidase A, were almost the same. This agreement between the apparent dissociation and inhibition constants indicates that the zinc binding to the enzymes directly relates to the inhibition of enzyme activity by excess zinc ions. Excess zinc ions were competitive inhibitors for both peptide and ester substrates. This behavior is believed to arise by the excess zinc ions fixing the enzyme in a conformation to which the substrates cannot bind.« less

Polaronic Charge Carrier-Lattice Interactions in Lead Halide Perovskites.

PubMed

Wolf, Christoph; Cho, Himchan; Kim, Young-Hoon; Lee, Tae-Woo

2017-10-09

Almost ten years after the renaissance of the popular perovskite-type semiconductors based on lead salts with the general formula AMX 3 (A=organic or inorganic cation; M=divalent metal; X=halide), many facets of photophysics continue to puzzle researchers. In this Minireview, light is shed on the low mobilities of charge carriers in lead halide perovskites with special focus on the lattice properties at non-zero temperature. The polar and soft lattice leads to pronounced electron-phonon coupling, limiting carrier mobility and retarding recombination. We propose that the proper picture of excited charge carriers at temperature ranges that are relevant for device operations is that of a polaron, with Fröhlich coupling constants between 1<α<3. Under the aspect of light-emitting diode application, APbX 3 perovskite show moderate second order (bimolecular) recombination rates and high third-order (Auger) rate constants. It has become apparent that this is a direct consequence of the anisotropic polar A-site cation in organic-inorganic hybrid perovskites and might be alleviated by replacing the organic moiety with an isotropic cation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electro-oxidation of the dye azure B: kinetics, mechanism, and by-products.

PubMed

Olvera-Vargas, Hugo; Oturan, Nihal; Aravindakumar, C T; Paul, M M Sunil; Sharma, Virender K; Oturan, Mehmet A

2014-01-01

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals ((•)OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by (•)OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19 × 10(9) M(-1) s(-1). It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.

A novel nitrite biosensor based on gold dendrites with egg white as template.

PubMed

He, Yaping; Zhang, Dawei; Dong, Sheying; Zheng, Jianbin

2012-01-01

Gold dendrites (AuD) were synthesized with egg white as the soft template and a novel nitrite (NO(2)(-)) biosensor was fabricated by assembly of a myoglobin (Mb)-L-cysteamine (Cys)-AuD biological hybrid. The results of Fourier transform infrared spectra and UV-visible spectra indicated that Mb retained its original structure in the resulting Mb-Cys-AuD. Electrochemical investigation of the biosensor showed a pair of well-defined, quasi-reversible redox peaks with E(pa) = -0.314 V and E(pc) = -0.344 V (vs. SCE) in 0.1 M, pH 7.0 sodium phosphate buffered saline at the scan rate of 200 mV/s. The transfer rate constant (k(s)) was 1.49 s(-1). The Mb-Cys-AuD showed a good electrochemical catalytic response for the reduction of NO(2)(-), with the linear range from 0.5 to 400 µM and the detection limit of 0.3 µM (S/N = 3). The apparent Michaelis-Menten constant (K(M)(app)) was estimated to be 0.2 mM. Therefore, the assembled bio-hybrid as a novel matrix opened up a further possibility for study on the design of enzymatic biosensors with potential applications.

Effect of flavonols on wine astringency and their interaction with human saliva.

PubMed

Ferrer-Gallego, Raúl; Brás, Natércia F; García-Estévez, Ignacio; Mateus, Nuno; Rivas-Gonzalo, Julián C; de Freitas, Victor; Escribano-Bailón, M Teresa

2016-10-15

The addition of external phenolic compounds to wines in order to improve their sensory quality is an established winemaking practice. This study was aimed at evaluating the effect of the addition of quercetin 3-O-glucoside on the astringency and bitterness of wines. Sensory results showed that the addition of this flavonol to wines results in an increase in astringency and bitterness. Additionally, flavonol-human salivary protein interactions were studied using fluorescence spectroscopy, dynamic light scattering and molecular dynamic simulations (MD). The apparent Stern-Volmer (KsvApp) and the apparent bimolecular quenching constants (kqApp) were calculated from fluorescence spectra. The KsvApp was 12620±390M(-1), and the apparent biomolecular constant was 3.94×10(12)M(-1)s(-1), which suggests that a complex was formed between the human salivary proteins and quercetin 3-O-glucoside. MD simulations showed that the quercetin 3-O-glucoside molecules have the ability to bind to the IB937 model peptide. Copyright © 2016 Elsevier Ltd. All rights reserved.

Micellar modification of drug stability: analysis of the effect of hexadecyltrimethylammonium halides on the rate of degradation of cephaclor.

PubMed

Oliveira, A G; Cuccovia, I M; Chaimovich, H

1990-01-01

The intra- and intermolecular rates of degradation of cephaclor were determined with and without hexadecyltrimethylammonium bromide (CTABr). Micellar-derived spectral shifts were used to measure the association of the ionic forms as well as to determine the effect of CTABr on the apparent acid dissociation constant of the antibiotic. The rate of degradation of cephaclor increased with detergent and was salt sensitive. Micellar effects were analyzed quantitatively within the framework of the pseudophase ion exchange model. All experimental data were fitted to this model which was used to predict the combined effects of pH and detergent concentration. Micelles increased the rate of OH- attack on cephaclor; most of the effect was due to the concentration of reagents in the micellar pseudophase. The intramolecular degradation was catalyzed 25-fold by micelles, and a working hypothesis to rationalize this effect is proposed. The results demonstrate that quantitative analysis can be utilized to assess and predict effects of detergents on drug stability.

Please Touch: Object Properties that Invite Touch.

PubMed

Klatzky, R L; Peck, J

2012-01-01

Touch has received increasing interest in marketing, given research indicating that contact with products influences evaluation and the tendency to purchase. However, little is known from the marketing or psychophysical literature about visible attributes of objects that elicit touch for hedonic purposes. In these studies, participants rated the tendency of pictured objects to invite touch, or "touch-ability." Rated touch-ability varied reliably with structural attributes of objects, and the structural influences were distinct from those on other ratings such as attractiveness and apparent expense. Although the trends varied across object sets, touch-ability generally declined as surface textures became markedly rough and shape complexity became extreme. Holding stimulus factors constant, touch-ability also varied with the specific hand movements that were anticipated. Finally, mean touch-ability ratings were correlated across participants with the "Need for Touch" scale, which measures an individual's tendency to touch products. The studies point to touch-ability as a potential factor that might be incorporated into product design.

The effect of fibre and gelatinised starch type on amylolysis and apparent viscosity during in vitro digestion at a physiological shear rate.

PubMed

Hardacre, Allan K; Yap, Sia-Yen; Lentle, Roger G; Monro, John A

2015-06-05

An in vitro system was used to determine if the addition of insoluble or soluble fibre to aqueous suspensions of gelatinised starch affected the rate at which the starch was digested. Pre-gelatinised potato or corn starch suspensions were digested with porcine pancreatic amylase in the presence of either finely milled insoluble fibres from various sources or with guar gum. In vitro digestion was conducted at 37°C in a rheometer at a low and constant shear rate of 10s(-1) and the quantity of glucose released measured. The rates of starch digestion and suspension viscosity declined asymptotically and were unaffected by the addition of wheat fibre, but were considerably reduced by the addition of wood and AllBran(®) fibre and to a much greater extent (60%) by the addition of guar. The latter effect may be due to inhibition of amylase activity by non starch polysaccharide sequences. Copyright © 2015 Elsevier Ltd. All rights reserved.

Dissolution of Uranium(IV) Oxide in Solutions of Ammonium Carbonate and Hydrogen Peroxide

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

Smith, Steven C.; Peper, Shane M.; Douglas, Matthew

2009-09-12

Understanding the dissolution characteristics of uranium oxides is of fundamental scientific interest. Bench scale experiments were conducted to determine the optimal dissolution parameters of uranium(IV) oxide (UO2) powder in solutions of ammonium carbonate [(NH4)2CO3] and hydrogen peroxide (H2O2). Experimental parameters included variable peroxide and carbonate concentrations, and temperature. Results indicate the dissolution rate of UO2 in 1 M (NH4)2CO3 increases linearly with peroxide concentration ranging from 0.05 – 2 M (1:1 to 40:1 mol ratio H2O2:U), with no apparent maximum rate reached under the limited conditions used in our study. Temperature ranging studies show the dissolution rate of UO2 inmore » 1 M (NH4)2CO3 and 0.1 M H2O2 (2:1 mol ratio H2O2:U) increases linearly from 15 °C to 60 °C, again with no apparent maximum rate reached. Dissolution of UO2 in solutions with constant [H2O2] and [(NH4)2CO3] ranging from 0.5 to 2 M showed no difference in rate; however dissolution was significantly reduced in 0.05 M (NH4)2CO3 solution. The results of this study demonstrate the influence of [H2O2], [(NH4)2CO3], and temperature on the dissolution of UO2 in peroxide-containing (NH4)2CO3 solutions. Future studies are planned to elucidate the solution and solid state complexes in these systems.« less

The effect of oxygen fugacity on the rheological evolution of crystallizing basaltic melts

NASA Astrophysics Data System (ADS)

Kolzenburg, S.; Di Genova, D.; Giordano, D.; Hess, K. U.; Dingwell, D. B.

2018-04-01

Storage and transport of silicate melts in the Earth's crust and their emplacement on the planet's surface occur almost exclusively at sub-liquidus temperatures. At these conditions, the melts undergo crystallization under a wide range of cooling-rates, deformation-rates, and oxygen fugacities (fO2). Oxygen fugacity is known to influence the thermodynamics and kinetics of crystallization in magmas and lavas. Yet, its influence on sub-liquidus rheology remains largely uncharted. We present the first rheological characterization of crystallizing lavas along natural cooling paths and deformation-rates and at varying fO2. Specifically, we report on apparent viscosity measurements for two crystallizing magmatic suspensions 1) at log ⁡ fO2 of -9.15 (quartz-fayalite-magnetite buffer, QFM, -2.1) and 2) in air. These fugacities span a range of reduced to oxidized conditions pertinent to magma migration and lava emplacement. We find that: 1) crystallization at constant cooling-rates results in a quasi-exponential increase in the apparent viscosity of the magmatic suspensions until they achieve their rheological cut off temperature (Tcutoff), where the melt effectively solidifies 2) the rheological departure and Tcutoff increase with increasing fO2 and 3) increasing fO2 results in decreased crystallization-rates. Based on the experimental results and by comparison with previous rheological isothermal studies we propose a generalisation of the effect of fO2 on the dynamic rheological evolution of natural magmatic and volcanic suspensions. We further discuss the implications for magmatic transport in plumbing and storage systems (e.g. conduits, dikes and magma chambers) and during lava flow emplacement.

Examining (239+240)Pu, (210)Pb and historical events to determine carbon, nitrogen and phosphorus burial in mangrove sediments of Moreton Bay, Australia.

PubMed

Sanders, Christian J; Santos, Isaac R; Maher, Damien T; Breithaupt, Joshua L; Smoak, Joseph M; Ketterer, Michael; Call, Mitchell; Sanders, Luciana; Eyre, Bradley D

2016-01-01

Two sediment cores were collected in a mangrove forest to construct geochronologies for the previous century using natural and anthropogenic radionuclide tracers. Both sediment cores were dated using (239+240)Pu global fallout signatures as well as (210)Pb, applying both the Constant Initial Concentration (CIC) and the Constant Rate of Supply (CRS) models. The (239+240)Pu and CIC model are interpreted as having comparable sediment accretion rates (SAR) below an apparent mixed region in the upper ∼5 to 10 cm. In contrast, the CRS dating method shows high sediment accretion rates in the uppermost intervals, which is substantially reduced over the lower intervals of the 100-year record. A local anthropogenic nutrient signal is reflected in the high total phosphorus (TP) concentration in younger sediments. The carbon/nitrogen molar ratios and δ(15)N values further support a local anthropogenic nutrient enrichment signal. The origin of these signals is likely the treated sewage discharge to Moreton Bay which began in the early 1970s. While the (239+240)Pu and CIC models can only produce rates averaged over the intervals of interest within the profile, the (210)Pb CRS model identifies elevated rates of sediment accretion, organic carbon (OC), nitrogen (N), and TP burial from 2000 to 2013. From 1920 to 2000, the three dating methods provide similar OC, N and TP burial rates, ∼150, 10 and 2 g m(-2) year(-1), respectively, which are comparable to global averages. Copyright © 2015 Elsevier Ltd. All rights reserved.

Rheology of surface granular flows

NASA Astrophysics Data System (ADS)

Orpe, Ashish V.; Khakhar, D. V.

Surface granular flow, comprising granular material flowing on the surface of a heap of the same material, occurs in several industrial and natural systems. The rheology of such a flow was investigated by means of measurements of velocity and number-density profiles in a quasi-two-dimensional rotating cylinder, half-filled with a model granular material monosize spherical stainless-steel particles. The measurements were made at the centre of the cylinder, where the flow is fully developed, using streakline photography and image analysis. The stress profile was computed from the number-density profile using a force balance which takes into account wall friction. Mean-velocity and root-mean-square (r.m.s.)-velocity profiles are reported for different particle sizes and cylinder rotation speeds. The profiles for the mean velocity superimpose when distance is scaled by the particle diameter d and velocity by a characteristic shear rate dot{gamma}_C = [gsin(beta_m-beta_s)/dcosbeta_s](1/2) and the particle diameter, where beta_m is the maximum dynamic angle of repose and beta_s is the static angle of repose. The maximum dynamic angle of repose is found to vary with the local flow rate. The scaling is also found to work for the r.m.s. velocity profiles. The mean velocity is found to decay exponentially with depth in the bed, with decay length lambda=1.1d. The r.m.s. velocity shows similar behaviour but with lambda=1.7d. The r.m.s. velocity profile shows two regimes: near the free surface the r.m.s. velocity is nearly constant and below a transition point it decays linearly with depth. The shear rate, obtained by numerical differentiation of the velocity profile, is not constant anywhere in the layer and has a maximum which occurs at the same depth as the transition in the r.m.s. velocity profile. Above the transition point the velocity distributions are Gaussian and below the transition point the velocity distributions gradually approach a Poisson distribution. The shear stress increases roughly linearly with depth. The variation in the apparent viscosity eta with r.m.s. velocity u shows a relatively sharp transition at the shear-rate maximum, and in the region below this point the apparent viscosity eta˜ u(-1.5) . The measurements indicate that the flow comprises two layers: an upper low-viscosity layer with a nearly constant r.m.s. velocity and a lower layer of increasing viscosity with a decreasing r.m.s. velocity. The thickness of the upper layer depends on the local flow rate and is independent of particle diameter while the reverse is found to hold for the lower-layer thickness. The experimental data is compared with the predictions of three models for granular flow.

Effect of extra-column volume on practical chromatographic parameters of sub-2-μm particle-packed columns in ultra-high pressure liquid chromatography.

PubMed

Wu, Naijun; Bradley, Ashley C; Welch, Christopher J; Zhang, Li

2012-08-01

Effects of extra-column volume on apparent separation parameters were studied in ultra-high pressure liquid chromatography with columns and inlet connection tubings of various internal diameters (id) using 50-mm long columns packed with 1.8-μm particles under isocratic conditions. The results showed that apparent retention factors were on average 5, 11, 18, and 41% lower than those corrected with extra-column volumes for 4.6-, 3.0-, 2.1-, and 1.0-mm id columns, respectively, when the extra-column volume (11.3 μL) was kept constant. Also, apparent pressures were 31, 16, 12, and 10% higher than those corrected with pressures from extra-column volumes for 4.6-, 3.0-, 2.1-, and 1.0-mm id columns at the respective optimum flow rate for a typical ultra-high pressure liquid chromatography system. The loss in apparent efficiency increased dramatically from 4.6- to 3.0- to 2.1- to 1.0-mm id columns, less significantly as retention factors increased. The column efficiency was significantly improved as the inlet tubing id was decreased for a given column. The results suggest that maximum ratio of extra-column volume to column void volume should be approximately 1:10 for column porosity more than 0.6 and a retention factor more than 5, where 80% or higher of theoretically predicted efficiency could be achieved. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Activation Energy of the Low-pH-Induced Lamellar to Bicontinuous Cubic Phase Transition in Dioleoylphosphatidylserine/Monoolein.

PubMed

Oka, Toshihiko; Saiki, Takahiro; Alam, Jahangir Md; Yamazaki, Masahito

2016-02-09

Electrostatic interaction is an important factor for phase transitions between lamellar liquid-crystalline (Lα) and inverse bicontinuous cubic (QII) phases. We investigated the effect of temperature on the low-pH-induced Lα to double-diamond cubic (QII(D)) phase transition in dioleoylphosphatidylserine (DOPS)/monoolein (MO) using time-resolved small-angle X-ray scattering with a stopped-flow apparatus. Under all conditions of temperature and pH, the Lα phase was directly transformed into an intermediate inverse hexagonal (HII) phase, and subsequently the HII phase slowly converted to the QII(D) phase. We obtained the rate constants of the initial step (i.e., the Lα to HII phase transition) and of the second step (i.e., the HII to QII(D) phase transition) using the non-negative matrix factorization method. The rate constant of the initial step increased with temperature. By analyzing this result, we obtained the values of its apparent activation energy, Ea (Lα → HII), which did not change with temperature but increased with an increase in pH. In contrast, the rate constant of the second step decreased with temperature at pH 2.6, although it increased with temperature at pH 2.7 and 2.8. These results indicate that the value of Ea (HII → QII(D)) at pH 2.6 increased with temperature, but the values of Ea (HII → QII(D)) at pH 2.7 and 2.8 were constant with temperature. The values of Ea (HII → QII(D)) were smaller than those of Ea (Lα → HII) at the same pH. We analyzed these results using a modified quantitative theory on the activation energy of phase transitions of lipid membranes proposed initially by Squires et al. (Squires, A. M.; Conn, C. E.; Seddon, J. M.; Templer, R. H. Soft Matter 2009, 5, 4773). On the basis of these results, we discuss the mechanism of this phase transition.

Mechanism of 1,4,5,8-naphthalene tetracarboxylic acid dianhydride hydrolysis and formation in aqueous solution.

PubMed

Barros, T C; Cuccovia, I M; Farah, J P S; Masini, J C; Chaimovich, H; Politi, M J

2006-01-07

The study of highly conjugated, carbonyl-containing molecules such as 1,4,5,8-naphthalene tetracarboxylic dianhydride, III, is of interest since reactivity differences and transmission of electronic effects through the conjugated framework can be evidenced. The kinetics of hydrolysis of III in aqueous solution were determined from 5 M acid to pH 10. In basic solution hydrolysis of III yields, sequentially, 1,4,5,8-naphthalene diacid monoanhydride, II, and 1,4,5,8-naphthalene tetracarboxylic acid, I. The second order rate constant for alkaline hydrolysis is 200 fold higher for the first ring opening. The water-catalyzed hydrolysis of III yields a pH-dependent mixture of ionic forms of I and II. The rate constant for water-catalyzed hydrolysis of III is 25 fold higher than that for II. In concentrated acid the rates for reaching equilibrium (I, II and III) increase and III is the major product. The pK(a)s of I (3.24, 5.13 and 6.25) and II (3.05, 5.90) were determined by potentiometric, fluorescence and UV spectroscopy titrations and by quantitative fit of the kinetic and equilibrium data. The apparent, pH-dependent, equilibrium constants, K(EqII), for anhydride formation between I and II were obtained from the UV spectra. The quantitative fit of kinetic and equilibrium data are consistent with the assumption that anhydride formation only proceeds with the fully protonated species for both I and II and permitted the estimation of the equilibrium constants for anhydride formation, K(EqII). The value of K(EqII) (I <==> II) between pH 1 and 6 was ca. 5. Geometry optimization calculations in the gas phase of the reactions of III in alkaline, neutral and acid conditions, at the DFT level of theory, gave electronic distributions that were qualitatively consistent with the experimental results.

Failure in laboratory fault models in triaxial tests

USGS Publications Warehouse

Savage, J.C.; Lockner, D.A.; Byerlee, J.D.

1996-01-01

A model of a fault in the Earth is a sand-filled saw cut in a granite cylinder subjected to a triaxial test. The saw cut is inclined at an angle a to the cylinder axis, and the sand filling is intended to represent gouge. The triaxial test subjects the granite cylinder to a constant confining pressure and increasing axial stress to maintain a constant rate of shortening of the cylinder. The required axial stress increases at a decreasing rate to a maximum, beyond which a roughly constant axial stress is sufficient to maintain the constant rate of shortening: Such triaxial tests were run for saw cuts inclined at angles ?? of 20??, 25??, 30??, 35??, 40??, 45??, and 50?? to the cylinder axis, and the apparent coefficient of friction ??a (ratio of the shear stress to the normal stress, both stresses resolved onto the saw cut) at failure was determined. Subject to the assumption that the observed failure involves slip on Coulomb shears (orientation unspecified), the orientation of the principal compression axis within the gouge can be calculated as a function of ??a for a given value of the coefficient of internal friction ??i. The rotation of the principal stress axes within the gouge in a triaxial test can then be followed as the shear strain across the gouge layer increases. For ??i ??? 0.8, an appropriate value for highly sheared sand, the observed values ??a imply that the principal-axis of compression within the gouge rotates so as to approach being parallel to the cylinder axis for all saw cut angles (20?? < ?? < 50??). In the limiting state (principal compression axis parallel to cylinder axis) the stress state in the gouge layer would be the same as that in the granite cylinder, and the failure criterion would be independent of the saw cut angle.

Mechanistic Studies of the Yeast Polyamine Oxidase Fms1: Kinetic Mechanism, Substrate Specificity, and pH Dependence†

PubMed Central

Adachi, Mariya S.; Torres, Jason M.; Fitzpatrick, Paul F.

2010-01-01

The flavoprotein oxidase Fms1 from Saccharomyces cerevisiae catalyzes the oxidation of spermine and N1-acetylspermine to yield spermidine and 3-aminopropanal or N-acetyl-3-aminopropanal. The kinetic mechanism of the enzyme has been determined with both substrates. The initial velocity patterns are ping-pong, consistent with reduction being kinetically irreversible. Reduction of Fms1 by either substrate is biphasic. The rate constant for the rapid phase varies with the substrate concentration, with limiting rates for reduction of the enzyme of 126 and 1410 s−1 and apparent Kd values of 24.3 and 484 μM for spermine and N1-acetylspermine, respectively. The rapid phase is followed by a concentration-independent phase that is slower than turnover. The reaction of the reduced enzyme with oxygen is monophasic, with a rate constant of 402 mM−1 s−1 with spermine at 25 °C, and 204 mM−1 s−1 with N1-acetylspermine at 4 °C, pH 9.0. This step is followed by rate-limiting product dissociation. The kcat/Kamine-pH profiles are bell-shaped, with an average pKa value of 9.3 with spermine and pKa values of 8.3 and 9.6 with N1-acetylspermine. Both profiles are consistent with the active forms of substrates having two charged nitrogens. The pH profiles for the rate constant for flavin reduction show pKa values of 8.3 and 7.2 for spermine and N1-acetylspermine, respectively, for groups that must be unprotonated; these pKa values are assigned to the substrate N4. The kcat/KO2-pH profiles show pKa values of 7.5 for spermine and 6.8 for N1-acetylspermine. With both substrates, the kcat value decreases when a single residue is protonated. PMID:21067138

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

Sawada, Y.; Kawai, R.; McManaway, M.

(3H)Cyclofoxy (CF: 17-cyclopropylmethyl-3,14-dihydroxy-4,5-alpha-epoxy-6-beta-fluoromorp hinan) is an opioid antagonist with affinity to both mu and kappa subtypes that was synthesized for quantitative evaluation of opioid receptor binding in vivo. Two sets of experiments in rats were analyzed. The first involved determining the metabolite-corrected blood concentration and tissue distribution of CF in brain 1 to 60 min after i.v. bolus injection. The second involved measuring brain washout for 15 to 120 s following intracarotid artery injection of CF. A physiologically based model and a classical compartmental pharmacokinetic model were compared. The models included different assumptions for transport across the blood-brain barrier (BBB);more » estimates of nonspecific tissue binding and specific binding to a single opiate receptor site were found to be essentially the same with both models. The nonspecific binding equilibrium constant varied modestly in different brain structures (Keq = 3-9), whereas the binding potential (BP) varied over a much broader range (BP = 0.6-32). In vivo estimates of the opioid receptor dissociation constant were similar for different brain structures (KD = 2.1-5.2 nM), whereas the apparent receptor density (Bmax) varied between 1 (cerebellum) and 78 (thalamus) pmol/g of brain. The receptor dissociation rate constants in cerebrum (k4 = 0.08-0.16 min-1; koff = 0.16-0.23 min-1) and brain vascular permeability (PS = 1.3-3.4 ml/min/g) are sufficiently high to achieve equilibrium conditions within a reasonable period of time. Graphical analysis of the data is inappropriate due to the high tissue-loss rate constant for CF in brain. From these findings, CF should be a very useful opioid receptor ligand for the estimation of the receptor binding parameters in human subjects using (18F)CF and positron emission tomography.« less

Complexation of Arsenite with Humic Acid in the Presence of Ferric Iron

PubMed Central

Liu, Guangliang; Fernandez, Aymara; Cai, Yong

2011-01-01

In the presence of iron (Fe), dissolved organic matter (DOM) may bind considerable amounts of arsenic (As), through formation of Fe-bridged As-Fe-DOM complexes and surface complexation of As on DOM-stabilized Fe-colloids (collectively referred to as As-Fe-DOM complexation). However, direct (e.g., chromatographic and spectroscopic) evidence and fundamental kinetic and stability constants have been rarely reported for this As-Fe-DOM complexation. Using a size exclusion chromatography (SEC)-UV-inductively coupled plasma mass spectrometry (ICP-MS) technique, arsenite (AsIII)-Fe-DOM complexation was investigated after adding AsIII into the priorly prepared Fe-DOM. A series of evidence, including coelution of As, Fe, and DOM from the SEC column and coretention of As, Fe, and DOM by 3 kDa MWCO centrifugal filtration membrane, demonstrated the occurrence of AsIII-Fe-DOM complexation. The kinetic data of AsIII-Fe-DOM complexation were well described by a pseudo-first order rate equation (R2 = 0.95), with the rate constant (k′) being 0.17±0.04 1/h. Stability of AsIII-Fe-DOM complexation was characterized by apparent stability constant (Ks) derived from two-site ligand binding model, with log Ks ranging from 4.4±0.2 to 5.6±0.4. Considering the kinetics (within hours) and stability (similar to typical metal-humates) of AsIII-Fe-DOM complexation, this complexation needs to be included when evaluating As mobility in Fe and DOM rich environments. PMID:21322632

Photochemical reaction of 2-(3-benzoylphenyl)propionic acid (ketoprofen) with basic amino acids and dipeptides.

PubMed

Suzuki, Tadashi; Shinoda, Mio; Osanai, Yohei; Isozaki, Tasuku

2013-08-22

Photoreaction of 2-(3-benzoylphenyl)propionic acid (ketoprofen, KP) with basic amino acids (histidine, lysine, and arginine) and dipeptides (carnosine and anserine) including a histidine moiety in phosphate buffer solution (pH 7.4) has been investigated with transient absorption spectroscopy. With UV irradiation KP(-) gave rise to a carbanion through a decarboxylation reaction, and the carbanion easily abstracted a proton from the surrounding molecule to yield a 3-ethylbenzophenone ketyl biradical (EBPH). The dipeptides as well as the basic amino acids were found to accelerate the proton transfer reaction whereas alanine and glycine had no effect on the reaction, revealing that these amino acids having a protonated side chain act as a proton donor. The formation quantum yield of EBPH was estimated to be fairly large by means of an actinometrical method with benzophenone, and the bimolecular reaction rate constant for the proton transfer between the carbanion and the protonated basic amino acids or the protonated dipeptides was successfully determined. It has become apparent that the bimolecular reaction rate constant for the proton transfer depended on the acid dissociation constant for the side chain of the amino acids for the first time. This reaction mechanism was interpreted by difference of the heat of reaction for each basic amino acid based on the thermodynamical consideration. These results strongly suggest that the side chain of the basic amino acid residue in protein should play an important role for photochemistry of KP in vivo.

Quantitative In Vitro and In Vivo Evaluation of Intestinal and Blood-Brain Barrier Transport Kinetics of the Plant N-Alkylamide Pellitorine.

PubMed

Veryser, Lieselotte; Bracke, Nathalie; Wynendaele, Evelien; Joshi, Tanmayee; Tatke, Pratima; Taevernier, Lien; De Spiegeleer, Bart

2016-01-01

Objective. To evaluate the gut mucosa and blood-brain barrier (BBB) pharmacokinetic permeability properties of the plant N-alkylamide pellitorine. Methods. Pure pellitorine and an Anacyclus pyrethrum extract were used to investigate the permeation of pellitorine through (1) a Caco-2 cell monolayer, (2) the rat gut after oral administration, and (3) the BBB in mice after intravenous and intracerebroventricular administration. A validated bioanalytical UPLC-MS(2) method was used to quantify pellitorine. Results. Pellitorine was able to cross the Caco-2 cell monolayer from the apical-to-basolateral and from the basolateral-to-apical side with apparent permeability coefficients between 0.6 · 10(-5) and 4.8 · 10(-5) cm/h and between 0.3 · 10(-5) and 5.8 · 10(-5) cm/h, respectively. In rats, a serum elimination rate constant of 0.3 h(-1) was obtained. Intravenous injection of pellitorine in mice resulted in a rapid and high permeation of pellitorine through the BBB with a unidirectional influx rate constant of 153 μL/(g·min). In particular, 97% of pellitorine reached the brain tissue, while only 3% remained in the brain capillaries. An efflux transfer constant of 0.05 min(-1) was obtained. Conclusion. Pellitorine shows a good gut permeation and rapidly permeates the BBB once in the blood, indicating a possible role in the treatment of central nervous system diseases.

Mechanistic Studies of Human Spermine Oxidase: Kinetic Mechanism and pH Effects†

PubMed Central

Adachi, Maria S.; Juarez, Paul R.; Fitzpatrick, Paul F.

2009-01-01

In mammalian cells, the flavoprotein spermine oxidase (SMO) catalyzes the oxidation of spermine to spermidine and 3-aminopropanal. Mechanistic studies have been carried out with the recombinant human enzyme. The initial velocity pattern when the ratio between the concentrations of spermine and oxygen is kept constant establishes the steady-state kinetic pattern as ping-pong. Reduction of SMO by spermine in the absence of oxygen is biphasic. The rate constant for the rapid phase varies with the substrate concentration, with a limiting value (k3) of 49 s−1 and an apparent Kd value of 48 µM at pH 8.3. The rate constant for the slow step is independent of the spermine concentration, with a value of 5.5 s−1, comparable to the kcat value of 6.6 s−1. The kinetics of the oxidative half-reaction depend on the aging time after spermine and enzyme are mixed in a double mixing experiment. At an aging time of 6 s the reaction is monophasic with a second order rate constant of 4.2 mM−1 s−1. At an aging time of 0.3 s the reaction is biphasic with two second order constants equal to 4.0 and 40 mM−1 s−1. Neither is equal to the kcat/KO2 value of 13 mM−1s−1. These results establish the existence of more than one pathway for the reaction of the reduced flavin intermediate with oxygen. The kcat/KM value for spermine exhibits a bell-shaped pH-profile, with an average pKa value of 8.3. This profile is consistent with the active form of spermine having three charged nitrogens. The pH profile for k3 shows a pKa value of 7.4 for a group that must be unprotonated. The pKi-pH profiles for the competitive inhibitors N,N’-dibenzylbutane-1,4-diamine and spermidine show that the fully protonated forms of the inhibitors and the unprotonated form of an amino acid residue with a pKa of about 7.4 in the active site are preferred for binding. PMID:20000632

Energy and calcium ion dependence of proteolysis during sporulation of Bacillus subtilis cells.

PubMed

O'Hara, M B; Hageman, J H

1990-08-01

Bacterial cells degrade intracellular proteins at elevated rates during starvation and can selectively degrade proteins by energy-dependent processes. Sporulating bacteria can degrade protein with apparent first-order rate constants of over 0.20 h-1. We have shown, with an optimized [14C]leucine-labeling and chasing procedure, in a chemically defined sporulation medium, that intracellular protein degradation in sporulating cells of Bacillus subtilis 168 (trpC2) is apparently energy dependent. Sodium arsenate, sodium azide, carbonyl cyanide m-chlorophenylhydrozone, and N,N'-dicyclohexylcarbodiimide, at levels which did not induce appreciable lysis (less than or equal to 10%) over 10-h periods of sporulation, inhibited intracellular proteolysis by 13 to 93%. Exponentially growing cells acquired arsenate resistance. In contrast to earlier reports, we found that chloramphenicol (100 micrograms/ml) strongly inhibited proteolysis (68%) even when added 6 h into the sporulation process. Restricting the calcium ion concentration (less than 2 microM) in the medium had no effect on rates or extent of vegetative growth, strongly inhibited sporulation (98%), and inhibited rates of proteolysis by 60% or more. Inhibitors of energy metabolism, at the same levels which inhibited proteolysis, did not affect the rate or degree of uptake of Ca2+ by cells, which suggested that the Ca2+ and metabolic energy requirements of proteolysis were independent. Restricting the Ca2+ concentration in the medium reduced by threefold the specific activity in cells of the major intracellular serine proteinase after 12 h of sporulation. Finally, cells of a mutant of B. subtilis bearing an insertionally inactivated gene for the Ca2(+)-dependent intracellular proteinase-1 degraded protein in chemically defined sporulation medium at a rate indistinguishable from that of the wild-type cells for periods of 8 h.

Photocatalytic degradation of carbofuran by TiO2-coated activated carbon: Model for kinetic, electrical energy per order and economic analysis.

PubMed

Vishnuganth, M A; Remya, Neelancherry; Kumar, Mathava; Selvaraju, N

2016-10-01

The photocatalytic removal of carbofuran (CBF) from aqueous solution in the presence of granular activated carbon supported TiO2 (GAC-TiO2) catalyst was investigated under batch-mode experiments. The presence of GAC enhanced the photocatalytic efficiency of the TiO2 catalyst. Experiments were conducted at different concentrations of CBF to clarify the dependence of apparent rate constant (kapp) in the pseudo first-order kinetics on CBF photodegradation. The general relationship between the adsorption equilibrium constant (K) and reaction rate constant (kr) were explained by using the modified Langmuir-Hinshelwood (L-H) model. From the observed kinetics, it was observed that the surface reaction was the rate limiting step in the GAC-TiO2 catalyzed photodegradation of CBF. The values of K and kr for this pseudo first-order reaction were found to be 0.1942 L  mg(-1) and 1.51 mg L(-1) min(-1), respectively. In addition, the dependence of kapp on the half-life time was determined by calculating the electrical energy per order experimentally (EEO experimental) and also by modeling (EEO model). The batch-mode experimental outcomes revealed the possibility of 100% CBF removal (under optimized conditions and at an initial concentration of 50 mg L(-1) and 100 mg L(-1)) at a contact time of 90 min and 120 min, respectively. Both L-H kinetic model and EEO model fitted well with the batch-mode experimental data and also elucidated successfully the phenomena of photocatalytic degradation in the presence of GAC-TiO2 catalyst. Copyright © 2016 Elsevier Ltd. All rights reserved.

Prediction of Rate Constant for Supramolecular Systems with Multiconfigurations.

PubMed

Guo, Tao; Li, Haiyan; Wu, Li; Guo, Zhen; Yin, Xianzhen; Wang, Caifen; Sun, Lixin; Shao, Qun; Gu, Jingkai; York, Peter; Zhang, Jiwen

2016-02-25

The control of supramolecular systems requires a thorough understanding of their dynamics, especially on a molecular level. It is extremely difficult to determine the thermokinetic parameters of supramolecular systems, such as drug-cyclodextrin complexes with fast association/dissociation processes by experimental techniques. In this paper, molecular modeling combined with novel mathematical relationships integrating the thermodynamic/thermokinetic parameters of a series of isomeric multiconfigurations to predict the overall parameters in a range of pH values have been employed to study supramolecular dynamics at the molecular level. A suitable form of Eyring's equation was derived and a two-stage model was introduced. The new approach enabled accurate prediction of the apparent dissociation/association (k(off)/k(on)) and unbinding/binding (k-r/kr) rate constants of the ubiquitous multiconfiguration complexes of the supramolecular system. The pyronine Y (PY) was used as a model system for the validation of the presented method. Interestingly, the predicted k(off) value ((40 ± 1) × 10(5) s(-1), 298 K) of PY is largely in agreement with that previously determined by fluorescence correlation spectroscopy ((5 ± 3) × 10(5) s(-1), 298 K). Moreover, the k(off)/k(on) and k-r/kr for flurbiprofen-β-cylcodextrin and ibuprofen-β-cyclodextrin systems were also predicted and suggested that the association processes are diffusion-controlled. The methodology is considered to be especially useful in the design and selection of excipients for a supramolecular system with preferred association and dissociation rate constants and understanding their mechanisms. It is believed that this new approach could be applicable to a wide range of ligand-receptor supramolecular systems and will surely help in understanding their complex mechanism.

Myosin dephosphorylation during rapid relaxation of hog carotid artery smooth muscle.

PubMed

Driska, S P; Stein, P G; Porter, R

1989-02-01

Changes in myosin light chain phosphorylation were measured during histamine-induced rhythmic contractions of hog carotid artery smooth muscle strips. Histamine made the muscle strips contract spontaneously every 1-5 min, and this allowed measurement of the time course of phosphorylation in relation to force development under conditions where diffusion of the agonist through tissue would not complicate the interpretation of the data. In the absence of histamine, phosphorylation was low [0.12 +/- 0.04 mol P/mol of the 20,000-Da light chain (LC 20)]. Phosphorylation was slightly (but not significantly) higher in the presence of 10 microM histamine in the relaxed state between contractions (0.20 +/- 0.03 mol P/mol LC 20). In muscle strips frozen during force development, when force had reached half of its peak value, phosphorylation was 0.38 +/- 0.06 mol P/mol LC 20. The highest levels of phosphorylation (0.49 +/- 0.04 mol P/mol LC 20) were found in strips frozen at the peak of the rhythmic contractions. Strips frozen when force had declined to half of the peak force showed low levels of phosphorylation (0.17 +/- 0.07 mol P/mol LC 20), indicating that the myosin light chain phosphatase activity was quite high. Mathematical modeling of the kinase and phosphatase reactions suggested that the apparent first-order phosphatase rate constant was at least 0.08 s-1 under these conditions. To obtain a better estimate of this rate constant, a second series of phosphorylation measurements were made early in the relaxation phase of the rhythmic contractions. The highest phosphatase rate constant obtained from these measurements was 0.23 s-1.(ABSTRACT TRUNCATED AT 250 WORDS)

Theoretical Bounds for the Influence of Tissue-Level Ductility on the Apparent-Level Strength of Human Trabecular Bone

PubMed Central

Nawathe, Shashank; Juillard, Frédéric; Keaveny, Tony M.

2015-01-01

The role of tissue-level post-yield behavior on the apparent-level strength of trabecular bone is a potentially important aspect of bone quality. To gain insight into this issue, we compared the apparent-level strength of trabecular bone for the hypothetical cases of fully brittle versus fully ductile failure behavior of the trabecular tissue. Twenty human cadaver trabecular bone specimens (5 mm cube; BV/TV = 6–36%) were scanned with micro-CT to create 3D finite element models (22-micron element size). For each model, apparent-level strength was computed assuming either fully brittle (fracture with no tissue ductility) or fully ductile (yield with no tissue fracture) tissue-level behaviors. We found that the apparent-level ultimate strength for the brittle behavior was only about half the value of the apparent-level 0.2%-offset yield strength for the ductile behavior, and the ratio of these brittle to ductile strengths was almost constant (mean ± SD = 0.56 ± 0.02; n=20; R2 = 0.99 between the two measures). As a result of this small variation, although the ratio of brittle to ductile strengths was positively correlated with the bone volume fraction (R2=0.44, p=0.01) and structure model index (SMI, R2=0.58, p<0.01), these effects were small. Mechanistically, the fully ductile behavior resulted in a much higher apparent-level strength because in this case about 16-fold more tissue was required to fail than for the fully brittle behavior; also, there was more tensile- than compressive-mode of failure at the tissue level for the fully brittle behavior. We conclude that, in theory, the apparent-level strength behavior of human trabecular bone can vary appreciably depending on whether the tissue fails in a fully ductile versus fully brittle manner, and this effect is largely constant despite appreciable variations in bone volume fraction and microarchitecture. PMID:23497799

Chemical transformation of 3-bromo-2,2-bis(bromomethyl)-propanol under basic conditions.

PubMed

Ezra, Shai; Feinstein, Shimon; Bilkis, Itzhak; Adar, Eilon; Ganor, Jiwchar

2005-01-15

The mechanism of the spontaneous decomposition of 3-bromo-2,2-bis(bromomethyl)propanol (TBNPA) and the kinetics of the reaction of the parent compound and two subsequent products were determined in aqueous solution at temperatures from 30 to 70 degrees C and pH from 7.0 to 9.5. TBNPA is decomposed by a sequence of reactions that form 3,3-bis(bromomethyl)oxetane (BBMO), 3-bromomethyl-3-hydroxymethyloxetane (BMHMO), and 2,6-dioxaspiro[3.3]-heptane (DOH), releasing one bromide ion at each stage. The pseudo-first-order rate constant of the decomposition of TBNPA increases linearlywith the pH. The apparent activation energy of this transformation (98+/-2 KJ/mol) was calculated from the change of the effective second-order rate constant with temperature. The pseudoactivation energies of BBMO and BMHMO were estimated to be 109 and 151 KJ/mol, respectively. Good agreement was found between the rate coefficients derived from changes in the organic molecules concentrations and those determined from the changes in the Br- concentrations. TBNPA is the most abundant semivolatile organic pollutant in the aquitard studied, and together with its byproducts they posess an environmental hazard. TBNPA half-life is estimated to be about 100 years. This implies that high concentrations of TBNPA will persist in the aquifer long after the elimination of all its sources.

The Arrhenius equation revisited.

PubMed

Peleg, Micha; Normand, Mark D; Corradini, Maria G

2012-01-01

The Arrhenius equation has been widely used as a model of the temperature effect on the rate of chemical reactions and biological processes in foods. Since the model requires that the rate increase monotonically with temperature, its applicability to enzymatic reactions and microbial growth, which have optimal temperature, is obviously limited. This is also true for microbial inactivation and chemical reactions that only start at an elevated temperature, and for complex processes and reactions that do not follow fixed order kinetics, that is, where the isothermal rate constant, however defined, is a function of both temperature and time. The linearity of the Arrhenius plot, that is, Ln[k(T)] vs. 1/T where T is in °K has been traditionally considered evidence of the model's validity. Consequently, the slope of the plot has been used to calculate the reaction or processes' "energy of activation," usually without independent verification. Many experimental and simulated rate constant vs. temperature relationships that yield linear Arrhenius plots can also be described by the simpler exponential model Ln[k(T)/k(T(reference))] = c(T-T(reference)). The use of the exponential model or similar empirical alternative would eliminate the confusing temperature axis inversion, the unnecessary compression of the temperature scale, and the need for kinetic assumptions that are hard to affirm in food systems. It would also eliminate the reference to the Universal gas constant in systems where a "mole" cannot be clearly identified. Unless proven otherwise by independent experiments, one cannot dismiss the notion that the apparent linearity of the Arrhenius plot in many food systems is due to a mathematical property of the model's equation rather than to the existence of a temperature independent "energy of activation." If T+273.16°C in the Arrhenius model's equation is replaced by T+b, where the numerical value of the arbitrary constant b is substantially larger than T and T(reference), the plot of Ln k(T) vs. 1/(T+b) will always appear almost perfectly linear. Both the modified Arrhenius model version having the arbitrary constant b, Ln[k(T)/k(T(reference)) = a[1/ (T(reference)+b)-1/ (T+b)], and the exponential model can faithfully describe temperature dependencies traditionally described by the Arrhenius equation without the assumption of a temperature independent "energy of activation." This is demonstrated mathematically and with computer simulations, and with reprocessed classical kinetic data and published food results.

Experimental studies of magnetite formation in the solar nebula

NASA Astrophysics Data System (ADS)

Hong, Y.; Fegley, B., Jr.

1998-09-01

Oxidation of Fe metal and Gibeon meteorite metal to magnetite via the net reaction 3 Fe (metal) + 4 H2O (gas) = Fe3O4 (magnetite) + 4 H2 (gas) was experimentally studied at ambient atmospheric pressure at 91-442oC in H2 and H2-He gas mixtures with H2/H2O molar ratios of ~4-41. The magnetite produced was identified by X-ray diffraction. Electron microprobe analyses showed 3.3 wt% NiO and 0.24 wt% CoO (presumably as NiFe2O4 and CoFe2O4) in magnetite formed from Gibeon metal. The NiO and CoO concentrations are higher than expected from equilibrium between metal and oxide under the experimental conditions. Elevated NiO contents in magnetite were also observed by metallurgists during initial stages of oxidation of Fe-Ni alloys. The rate constants for magnetite formation were calculated from the weight gain data using a constant surface area model and the Jander, Ginstling-Brounshtein, and Valensi-Carter models for powder reactions. Magnetite formation followed parabolic (i.e., diffusion controlled) kinetics. The rate constants and apparent activation energies for Fe metal and Gibeon metal are: cm2 hour-1 Eact = 92=B15(2s) kJ mol-1 cm2 hour-1 Eact = 95=B112(2s) kJ mol-1 These rate constants are significantly smaller than the parabolic rate constants for FeS growth on Fe metal in H2S-H2 gas mixtures containing 1000 or 10,000 ppmv H2S (Lauretta et al. 1996a). The experimental data for Fe and Gibeon metal are used to model the reaction time of Fe alloy grains in the solar nebula as a function of grain size and temperature. The reaction times for 0.1-1 micron radius metal grains are generally within estimated lifetimes of the solar nebula (0.1-10 million years). However, the calculated reaction times are probably lower limits and further study of magnetite formation at larger H2/H2O ratios, at lower temperatures and pressures, and as a function of metal alloy composition is needed for further modeling of nebular magnetite formation.

Population pharmacokinetics and maximum a posteriori probability Bayesian estimator of abacavir: application of individualized therapy in HIV-infected infants and toddlers

PubMed Central

Zhao, Wei; Cella, Massimo; Della Pasqua, Oscar; Burger, David; Jacqz-Aigrain, Evelyne

2012-01-01

AIMS To develop a population pharmacokinetic model for abacavir in HIV-infected infants and toddlers, which will be used to describe both once and twice daily pharmacokinetic profiles, identify covariates that explain variability and propose optimal time points to optimize the area under the concentration–time curve (AUC) targeted dosage and individualize therapy. METHODS The pharmacokinetics of abacavir was described with plasma concentrations from 23 patients using nonlinear mixed-effects modelling (NONMEM) software. A two-compartment model with first-order absorption and elimination was developed. The final model was validated using bootstrap, visual predictive check and normalized prediction distribution errors. The Bayesian estimator was validated using the cross-validation and simulation–estimation method. RESULTS The typical population pharmacokinetic parameters and relative standard errors (RSE) were apparent systemic clearance (CL) 13.4 l h−1 (RSE 6.3%), apparent central volume of distribution 4.94 l (RSE 28.7%), apparent peripheral volume of distribution 8.12 l (RSE14.2%), apparent intercompartment clearance 1.25 l h−1 (RSE 16.9%) and absorption rate constant 0.758 h−1 (RSE 5.8%). The covariate analysis identified weight as the individual factor influencing the apparent oral clearance: CL = 13.4 × (weight/12)1.14. The maximum a posteriori probability Bayesian estimator, based on three concentrations measured at 0, 1 or 2, and 3 h after drug intake allowed predicting individual AUC0–t. CONCLUSIONS The population pharmacokinetic model developed for abacavir in HIV-infected infants and toddlers accurately described both once and twice daily pharmacokinetic profiles. The maximum a posteriori probability Bayesian estimator of AUC0–t was developed from the final model and can be used routinely to optimize individual dosing. PMID:21988586

Characterization of Actinides Complexed to Nuclear Fuel Constituents Using ESI-MS

DOE PAGES

McDonald, Luther W.; Campbell, James A.; Vercouter, Thomas; ...

2016-03-01

Electrospray ionization-mass spectrometry (ESI-MS) was tested for its use in monitoring spent nuclear fuel (SNF) constituents including U, Pu, dibutyl phosphate (DBP), and tributyl phosphate (TBP). Both positive and negative ion modes were used to evaluate the speciation of U and Pu with TBP and DBP. Furthermore, apparent stability constants were determined for U complexed to TBP and DBP. In positive ion mode, TBP produced a strong signal with and without complexation to U or Pu, but, in negative ion mode, no TBP, U-TBP, or Pu-TBP complexes were observed. Apparent stability constants were determined for [UO 2(NO 3) 2(TBP) 2],more » [UO 2(NO 3) 2(H 2O)(TBP) 2], and [UO 2(NO 3) 2(TBP) 3]. In contrast DBP, U-DBP, and Pu-DBP complexes were observed in both positive and negative ion modes. Apparent stability constants were determined for the species [UO 2(DBP)], [UO 2(DBP) 3], and [UO 2(DBP) 4]. Analyzing mixtures of U or Pu with TBP and DBP yielded the formation of ternary complexes whose stoichiometry was directly related to the ratio of TBP to DBP. The ESI-MS protocols used in this study will further demonstrate the utility of ESI-MS and its applicability to process control monitoring in SNF reprocessing facilities.« less

Observations of instability, hysteresis, and oscillation in low-Reynolds-number flow past polymer gels.

PubMed

Eggert, Matthew D; Kumar, Satish

2004-10-01

We perform a set of experiments to study the nonlinear nature of an instability that arises in low-Reynolds-number flow past polymer gels. A layer of a viscous liquid is placed on a polydimethylsiloxane (PDMS) gel in a parallel-plate rheometer which is operated in stress-controlled mode. As the shear stress on the top plate increases, the apparent viscosity stays relatively constant until a transition stress where it sharply increases. If the stress is held at a level slightly above the transition stress, the apparent viscosity oscillates with time. If the stress is increased to a value above the transition stress and then decreased back to zero, the apparent viscosity shows hysteretic behavior. If the stress is instead decreased to a constant value and held there, the apparent viscosity is different from its pretransition value and exhibits sustained oscillations. This can happen even if the stress is held at values below the transition stress. Our observations suggest that the instability studied here is subcritical and leads to a flow that is oscillatory and far from viscometric. The phenomena reported here may be useful in applications such as microfluidics, membrane separations, and polymer processing. They may also provide insight into the rheological behavior of complex fluids that undergo flow-induced gelation.

Photocatalytic degradation of p,p'-DDT under UV and visible light using interstitial N-doped TiO₂.

PubMed

Ananpattarachai, Jirapat; Kajitvichyanukul, Puangrat

2015-01-01

1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (or p,p'-DDT) is one of the most persistent pesticides. It is resistant to breakdown in nature and cause the water contamination problem. In this work, a major objective was to demonstrate the application of N-doped TiO2 in degradation and mineralization of the p,p'-DDT under UV and visible light in aqueous solution. The N-doped TiO2 nanopowders were prepared by a simple modified sol-gel procedure using diethanolamine (DEA) as a nitrogen source. The catalyst characteristics were investigated using XRD, SEM, TEM, and XPS. The adsorption and photocatalytic oxidation of p,p'-DDT using the synthesized N-doped TiO2 under UV and visible light were conducted in a batch photocatalytic experiment. The kinetics and p,p'-DDT degradation performance of the N-doped TiO2 were evaluated. Results show that the N-doped TiO2 can degrade p,p'-DDT effectively under both UV and visible lights. The rate constant of the p,p'-DDT degradation under UV light was only 0.0121 min(-1), whereas the rate constant of the p,p'-DDT degradation under visible light was 0.1282 min(-1). Under visible light, the 100% degradation of p,p'-DDT were obtained from N-doped TiO2 catalyst. The reaction rate of p,p'-DDT degradation using N-doped TiO2 under visible light was sixfold higher than that under UV light. According to Langmuir-Hinshelwood model, the adsorption equilibrium constant (K) for the N-doped TiO2 under visible light was 0.03078 L mg(-1), and the apparent reaction rate constant (k) was 1.3941 mg L(-1)-min. Major intermediates detected during the p,p'-DDT degradation were p,p'-DDE, o,p'-DDE, p,p'-DDD and p,p'-DDD. Results from this work can be applied further for the breakdown of p,p'-DDT molecule in the real contaminated water using this technology.

Preliminary characterization of persisting circadian rhythms during space flight

NASA Technical Reports Server (NTRS)

Sultzman, F. M.

1984-01-01

In order to evaluate the function of the circadian timing system in space, the circadian rhythm of conidiation of the fungus Neurospora crassa was monitored in constant darkness on the STS 9 flight of the Space Shuttle Columbia. During the first 7 days of spaceflight many tubes showed a marked reduction in the apparent amplitude of the conidiation rhythm, and some cultures appeared arrhythmic. There was more variability in the growth rate and circadian rhythms of individual cultures in space than is usually seen on earth. The results of this experiment indicate that while the circadian rhythm of Neurospora conidiation can persist outside of the earth's environment, either the timekeeping process or its expression is altered in space.

Mechanism-based pharmacodynamic modeling of the interaction of midazolam, bretazenil, and zolpidem with ethanol.

PubMed

Tuk, Bert; van Gool, Toon; Danhof, Meindert

2002-06-01

The pharmacokinetic and pharmacodynamic interactions of ethanol with the full benzodiazepine agonist midazolam, the partial agonist bretazenil and the benzodiazepine BZ1 receptor subtype selective agonist zolpidem have been determined in the rat in vivo, using an integrated pharmacokinetic-pharmacodynamic approach. Ethanol was administered as a constant rate infusion resulting in constant plasma concentrations of 0.5 g/l. The pharmacokinetics and pharmacodynamics of midazolam, bretazenil, and zolpidem were determined following an intravenous infusion of 5.0, 2.5, and 18 mg/kg respectively. The amplitude in the 11.5-30 Hz frequency band of the EEG was used as measure of the pharmacological effect. For each of the benzodiazepines the concentration-EEG effect relationship could be described by the sigmoid Emax pharmacodynamic model. Significant differences in both EC50 and Emax were observed. The values of the EC50 were 76 +/- 11, 12 +/- 3, and 512 +/- 116 ng/ml for midazolam, bretazenil, and zolpidem respectively. The values of the Emax were 113 +/- 9, 44 +/- 3, and 175 +/- 10 microV/s. In the presence of ethanol the values of the EC50 of midazolam and zolpidem were reduced to approximately 50% of the original value. The values for Emax and Hill-factor were unchanged Due to a large interindividual variability no significant change in EC50 was observed for bretazenil. Analysis of the data on basis of a mechanism-based model showed only a decrease in the apparent affinity constant KPD for all three drugs, indicating that changes in EC50 can be explained entirely by a change in the apparent affinity constant KPD without concomitant changes in the efficacy parameter ePD and the stimulus-effect relationship. The findings of this study show that the pharmacodynamic interactions with a low dose of ethanol in vivo are qualitatively and quantitatively similar for benzodiazepine receptor full agonists, partial agonists, and benzodiazepine BZ1 receptor subtype selective agonists. This interaction can be explained entirely by a change in the affinity of the biological system for each benzodiazepine.

Combined Diffusion Tensor Imaging and Apparent Transverse Relaxation Rate Differentiate Parkinson Disease and Atypical Parkinsonism.

PubMed

Du, G; Lewis, M M; Kanekar, S; Sterling, N W; He, L; Kong, L; Li, R; Huang, X

2017-05-01

Both diffusion tensor imaging and the apparent transverse relaxation rate have shown promise in differentiating Parkinson disease from atypical parkinsonism (particularly multiple system atrophy and progressive supranuclear palsy). The objective of the study was to assess the ability of DTI, the apparent transverse relaxation rate, and their combination for differentiating Parkinson disease, multiple system atrophy, progressive supranuclear palsy, and controls. A total of 106 subjects (36 controls, 35 patients with Parkinson disease, 16 with multiple system atrophy, and 19 with progressive supranuclear palsy) were included. DTI and the apparent transverse relaxation rate measures from the striatal, midbrain, limbic, and cerebellar regions were obtained and compared among groups. The discrimination performance of DTI and the apparent transverse relaxation rate among groups was assessed by using Elastic-Net machine learning and receiver operating characteristic curve analysis. Compared with controls, patients with Parkinson disease showed significant apparent transverse relaxation rate differences in the red nucleus. Compared to those with Parkinson disease, patients with both multiple system atrophy and progressive supranuclear palsy showed more widespread changes, extending from the midbrain to striatal and cerebellar structures. The pattern of changes, however, was different between the 2 groups. For instance, patients with multiple system atrophy showed decreased fractional anisotropy and an increased apparent transverse relaxation rate in the subthalamic nucleus, whereas patients with progressive supranuclear palsy showed an increased mean diffusivity in the hippocampus. Combined, DTI and the apparent transverse relaxation rate were significantly better than DTI or the apparent transverse relaxation rate alone in separating controls from those with Parkinson disease/multiple system atrophy/progressive supranuclear palsy; controls from those with Parkinson disease; those with Parkinson disease from those with multiple system atrophy/progressive supranuclear palsy; and those with Parkinson disease from those with multiple system atrophy; but not those with Parkinson disease from those with progressive supranuclear palsy, or those with multiple system atrophy from those with progressive supranuclear palsy. DTI and the apparent transverse relaxation rate provide different but complementary information for different parkinsonisms. Combined DTI and apparent transverse relaxation rate may be a superior marker for the differential diagnosis of parkinsonisms. © 2017 by American Journal of Neuroradiology.

Dielectric properties of CaCu3Ti4O12-silicone resin composites

NASA Astrophysics Data System (ADS)

Babu, Sanjesh; Singh, Kirti; Govindan, Anil

2012-06-01

CaCu3Ti4O12 (CCTO)-silicone resin composites with various CCTO volume fractions were prepared. Relatively high dielectric constant ( ɛ=119) and low loss (tan δ=0.35) of the composites with CCTO volume fraction of 0.9 were observed. Two theoretical models were employed to predict the dielectric constant of these composites; the dielectric constant obtained via the Maxwell-Garnett model was in close agreement with the experimental data. The dielectric constant of CCTO-silicone resin composites showed a weak frequency dependence at the measuring frequency range and the loss tangent apparently decreases with increase in frequency.

Measuring Positive Cooperativity Using the Direct ESI-MS Assay. Cholera Toxin B Subunit Homopentamer Binding to GM1 Pentasaccharide

NASA Astrophysics Data System (ADS)

Lin, Hong; Kitova, Elena N.; Klassen, John S.

2014-01-01

Direct electrospray ionization mass spectrometry (ESI-MS) assay was used to investigate the stepwise binding of the GM1 pentasaccharide β- D-Gal p-(1→3)-β-D-Gal pNAc-(1→4)[α-D-Neu5Ac-(2→3)]-β- D-Gal p-(1→4)-β-D-Glc p (GM1os) to the cholera toxin B subunit homopentamer (CTB5) and to establish conclusively whether GM1os binding is cooperative. Apparent association constants were measured for the stepwise addition of one to five GM1os to CTB5 at pH 6.9 and 22 °C. The intrinsic association constant, which was established from the apparent association constant for the addition of a single GM1os to CTB5, was found to be (3.2 ± 0.2) × 106 M-1. This is in reasonable agreement with the reported value of (6.4 ± 0.3) × 106 M-1, which was measured at pH 7.4 and 25 °C using isothermal titration calorimetry (ITC). Analysis of the apparent association constants provides direct and unambiguous evidence that GM1os binding exhibits small positive cooperativity. Binding was found to be sensitive to the number of ligand-bound nearest neighbor subunits, with the affinities enhanced by a factor of 1.7 and 2.9 when binding occurs next to one or two ligand-bound subunits, respectively. These findings, which provide quantitative support for the binding model proposed by Homans and coworkers [14], highlight the unique strengths of the direct ESI-MS assay for measuring cooperative ligand binding.

Discovery of a remarkable subpulse drift pattern in PSR B0818-41

NASA Astrophysics Data System (ADS)

Bhattacharyya, B.; Gupta, Y.; Gil, J.; Sendyk, M.

2007-05-01

We report the discovery of a remarkable subpulse drift pattern in the relatively less-studied wide profile pulsar B0818-41 using high-sensitivity Giant Metrewave Radio Telescope (GMRT) observations. We find simultaneous occurrences of three drift regions with two different drift rates: an inner region with steeper apparent drift rate flanked on each side by a region of slower apparent drift rate. Furthermore, these closely spaced drift bands always maintain a constant phase relationship. Though these drift regions have significantly different values for the measured P2, the measured P3 value is the same and equal to 18.3P1. We interpret the unique drift pattern of this pulsar as being created by the intersection of our line of sight (LOS) with two conal rings on the polar cap of a fairly aligned rotator (inclination angle α ~ 11°), with an `inner' LOS geometry (impact angle ). We argue that both rings have the same values for the carousel rotation periodicity P4 and the number of sparks Nsp. We find that Nsp is 19-21 and show that it is very likely that P4 is the same as the measured P3, making it a truly unique pulsar. We present results from simulations of the radiation pattern using the inferred parameters, which support our interpretations and reproduce the average profile as well as the observed features in the drift pattern quite well.

Discovery of remarkable subpulse drifting pattern in PSR B0818-41

NASA Astrophysics Data System (ADS)

Bhattacharyya, B.; Gupta, Y.; Gil, J.; Sendyk, M.

The study of pulsars showing systematic subpulse drift patterns provides important clues for understanding of pulsar emission mechanism. Pulsars with wide profiles provide extra insights because of the presence of multiple drift bands (e.g PSR B0826-34). We report the discovery of a remarkable subpulse drift pattern in a relatively less studied wide profile pulsar, PSR B0818-41, using the GMRT. We find simultaneous occurrence of three drift regions with two drift rates, an inner region with steeper apparent drift rate flanked on each side by a region of slower apparent drift rate. Furthermore, the two closely spaced drift regions always maintain a constant phase relationship. These unique drift properties seen for this pulsar is very rare. We interpret that the observed drift pattern is created by intersection of our line of sight (LOS) with two conal rings in a inner LOS (negative beta) geometry. We argue that the carousel rotation periodicity (P_4) and the number of sparks (N_sp) are the same for the rings and claim that P_4 is close to the measured P_3. Based on our analysis results and interpretations, we simulate the radiation from B0818-41. The simulations support our interpretations and reproduce the average profile and the observed drift pattern. The results of our study show that PSR B0818-41 is a powerful system to explore the pulsar radio emission mechanism, the implications of which are also discussed in our work.

Non-destructive testing principles and accurate evaluation of the hydraulic measure impact range using the DC method

NASA Astrophysics Data System (ADS)

Qiu, Liming; Shen, Rongxi; Song, Dazhao; Wang, Enyuan; Liu, Zhentang; Niu, Yue; Jia, Haishan; Xia, Shankui; Zheng, Xiangxin

2017-12-01

An accurate and non-destructive evaluation method for the hydraulic measure impact range in coal seams is urgently needed. Aiming at the application demands, a theoretical study and field test are presented using the direct current (DC) method to evaluate the impact range of coal seam hydraulic measures. We firstly analyzed the law of the apparent resistivity response of an abnormal conductive zone in a coal seam, and then investigated the principle of non-destructive testing of the coal seam hydraulic measure impact range using the DC method, and used an accurate evaluation method based on the apparent resistivity cloud chart. Finally, taking hydraulic fracturing and hydraulic flushing as examples, field experiments were carried out in coal mines to evaluate the impact ranges. The results showed that: (1) in the process of hydraulic fracturing, coal conductivity was enhanced by high-pressure water in the coal seam, and after hydraulic fracturing, the boundary of the apparent resistivity decrease area was the boundary impact range. (2) In the process of hydraulic flushing, coal conductivity was reduced by holes and cracks in the coal seam, and after hydraulic flushing, the boundary of the apparent resistivity increase area was the boundary impact range. (3) After the implementation of the hydraulic measures, there may be some blind zones in the coal seam; in hydraulic fracturing blind zones, the apparent resistivity increased or stayed constant, while in hydraulic flushing blind zones, the apparent resistivity decreased or stayed constant. The DC method realized a comprehensive and non-destructive evaluation of the impact range of the hydraulic measures, and greatly reduced the time and cost of evaluation.

pH regulation in barnacle muscle fibers: dependence on extracellular sodium and bicarbonate.

PubMed

Boron, W F; McCormick, W C; Roos, A

1981-01-01

Intracellular pH (pHi) regulation was studied in barnacle muscle fibers with pH-sensitive microelectrodes. The cells were acid loaded, and the subsequent recovery of pHi was monitored. The rate of recovery was reduced by one-third when external Na+ ([Na+]o) was replaced by Li+, but recovery was completely abolished when Na+ was replaced by choline or N-methyl-D-glucamine. In other experiments, varying amounts of Na+ were replaced by choline, and the acid extrusion rate, derived from the recovery rate of pHi, was calculated at a single value of pHi, 6.80. The dependence of the acid extrusion rate on [Na+]o could be described by Michaelis-Menten kinetics; at pHo (extracellular) = 8.0 and [HCO3-]o (extracellular) = 10 mM, the apparent Km and Vmax were 59 mM and 1.3 mmol x l(-1) x min-1. When [HCO3-]o was reduced to 2.5 mM at the same pHo, Km did not change significantly, but Vmax was substantially reduced. On the other hand, when pHo was reduced to 7.4 at constant [HCO3-]o, Vmax changed only slightly, but Km increased substantially. In similar experiments, we examined the dependence of the acid extrusion rate on [HCO3-]o. At pHo = 8.0 and [Na+]o = 440 mM, the apparent Km and Vmax were 4.1 mM and 2.1 mmol x 1-1 x min-1. When pHo was reduced to 7.4, Vmax was not altered, but Km substantially increased. The kinetic data are discussed in terms of the role of pHo, [Na+]o, and [HCO3-]o in the pHi-regulating system.

Pharmacological characterization of extracellular acidification rate responses in human D2(long), D3 and D4.4 receptors expressed in Chinese hamster ovary cells

PubMed Central

Coldwell, M C; Boyfield, I; Brown, A M; Stemp, G; Middlemiss, D N

1999-01-01

This study characterized pharmacologically the functional responses to agonists at human dopamine D2(long) (hD2), D3 (hD3) and D4.4 (hD4) zreceptors separately expressed in cloned cells using the cytosensor microphysiometer. Dopaminergic receptor agonists caused increases in extracellular acidification rate in adherent Chinese hamster ovary (CHO) clones expressing hD2, hD3 or hD4 receptors. Acidification rate responses to agonists in other cell lines expressing these receptors were smaller than those in adherent CHO cells. The time courses and maximum increases in acidification rate of the agonist responses in adherent CHO cells were different between the three dopamine receptor clones. Responses were blocked by pretreatment of cells with pertussis toxin or amiloride analogues. Most agonists had full intrinsic activity at each of the dopamine receptor subtypes, as compared to quinpirole, however both enantiomers of UH-232 and (−)3-PPP were partial agonists in this assay system. The functional potency of full agonists at each of the three receptors expressed in CHO cells was either higher than, or similar to, the apparent inhibition constants (Ki) determined in [125I]-iodosulpride competition binding studies. Functional selectivities of the agonists were less than radioligand binding selectivities. The rank orders of agonist potencies and selectivities were similar, but not identical, to the rank orders of radioligand binding affinities and selectivities. The dopamine receptor antagonists, iodosulpride and clozapine, had no effect on basal acidification rates but inhibited acidification responses in CHO cells to quinpirole in an apparently competitive manner. Antagonist potencies closely matched their radioligand binding affinities in these cells. PMID:10455259

Increased frequency of chloroquine resistant P. falciparum on a rubber estate in Peninsular Malaysia during two years of systematic chloroquine treatment.

PubMed

Dondero, T J; Parsons, R E; O'Holohan, D R

1975-12-01

Chloroquine pressure was applied over a 22 month period on a somewhat isolated, malarious rubber estate by examination of residents at 4-week intervals and treatment of parasitaemias with chloroquine. During this time the monthly attack rate for P. falciparum rose four-fold to an average of nearly 18% per month, while that of P. vivax remained relatively constant at about 8%. Eight in vivo chloroquine resistance studies, which allowed both detection of late recrudescing R-I resistance and estimation of the risk of reinfection, showed an apparent rise in the drug resistance rate, from 12% to 20% prior to the study to the range of 40-50%. Virtually all resistance encountered was R-I in nature. There was no convincing evidence of chloroquine resistance among 148 tested P. vivax infections.

Potential of pressure solution for strain localization in the Baccu Locci Shear Zone (Sardinia, Italy)

NASA Astrophysics Data System (ADS)

Casini, Leonardo; Funedda, Antonio

2014-09-01

The mylonites of the Baccu Locci Shear Zone (BLSZ), Sardinia (Italy), were deformed during thrusting along a bottom-to-top strain gradient in lower greenschist facies. The microstructure of metavolcanic protoliths shows evidence for composite deformation accommodated by dislocation creep within strong quartz porphyroclasts, and pressure solution in the finer grained matrix. The evolution of mylonite is simulated in two sets of numerical experiments, assuming either a constant width of the deforming zone (model 1) or a narrowing shear zone (model 2). A 2-5 mm y-1 constant-external-velocity boundary condition is applied on the basis of geologic constraints. Inputs to the models are provided by inverting paleostress values obtained from quartz recrystallized grain-size paleopiezometry. Both models predict a significant stress drop across the shear zone. However, model 1 involves a dramatic decrease in strain rate towards the zone of apparent strain localization. In contrast, model 2 predicts an increase in strain rate with time (from 10-14 to 10-12 s-1), which is consistent with stabilization of the shear zone profile and localization of deformation near the hanging wall. Extrapolating these results to the general context of crust strength suggests that pressure-solution creep may be a critical process for strain softening and for the stabilization of deformation within shear zones.

Fabrication of copper decorated tungsten oxide-titanium oxide nanotubes by photochemical deposition technique and their photocatalytic application under visible light

NASA Astrophysics Data System (ADS)

Momeni, Mohamad Mohsen

2015-12-01

Copper decorated WO3-TiO2 nanotubes (Cu/WTNs) with a high photocatalytic activity were prepared by anodizing and photochemical deposition. Highly ordered WO3-TiO2 nanotubes (WTNs) on pure titanium foils were successfully fabricated by electrochemical anodizing and copper deposited on these nanotubes (Cu/WTNs) by photoreduction method. The resulting samples were characterized by various methods. Only the anatase phase was detected by X-ray diffraction analysis. The presence of copper in the structure of thin films was confirmed by energy dispersive X-ray spectrometry and X-ray diffraction. The extension of optical absorption into the visible region of as-prepared films was indicated by UV/Vis spectroscopy. The degradation of methylene blue was used as a model reaction to evaluate the photocatalytic activity of the obtained samples. Results showed that the photocatalytic activity of Cu/WTNs samples is higher than bare WTNs sample. Kinetic research showed that the reaction rate constant of Cu/WTNs is approximately 2.5 times higher than the apparent reaction rate constant of bare WTNs. These results not only offer an economical method for constructing Cu/WTNs photocatalysts, but also shed new insight on the rational design of a low cost and high-efficiency photocatalyst for environmental remediation.

Influence of substrate structure on turnover of the organic cation/H+ exchanger of the renal luminal membrane.

PubMed

Wright, S H; Wunz, T M

1998-08-01

We examined the influence of organic cation (OC) structure on the rate of turnover of the OC/H+ exchanger in rabbit renal brush-border membrane vesicles (BBMV). The rate of efflux of [14C]tetraethylammonium ([14C]TEA) from BBMV, measured in the presence of an inwardly directed chemical gradient for test agent, provided an indirect measure of activity of the OC/H+(OC) exchanger. The trans-stimulation of [14C]TEA efflux from BBMV was a saturable function of increasing extravesicular concentration of both unlabeled TEA and tetramethylammonium (TMA), with an apparent Michaelis constant (Kt) for the interaction of these compounds with the OC/H+(OC) exchanger of 25 microM and 1 mM, respectively. The effect on [14C]TEA efflux of saturating extravesicular concentrations of a series of n-tetraalkylammonium compounds was examined. Whereas the short-chain compounds TMA and TEA markedly stimulated [14C]TEA efflux (by 830% and 690%, respectively), the long-chain compounds tetrapropylammonium and tetrabutylammonium were less effective, increasing efflux by only 40% and 120%, respectively. When the exchanger was saturated with tetrapentylammonium, mediated efflux of [14C]TEA was reduced. Increasing alkyl chain length was also correlated with an increase in the inhibitory effect (as measured by the apparent inhibition constant, Ki, or the IC50 value) that these compounds had against transport of [14C]TEA by the OC/H+(OC) exchanger; i.e., there was a correlation between decreasing IC50 and decreasing turnover of the OC/H+(OC) exchanger. This same correlation was observed for a broader set of test agents of diverse molecular structure, including a series of n-tetraalkylammonium and -phosphonium compounds and the OCs, choline, N1-methyl nicotinamide, 1-methyl-4-phenylpyridinium, and amiloride. Because high affinity of substrates for the OC/H+(OC) exchanger is correlated with increasing substrate hydrophobicity, we conclude that the interaction of hydrophobic OCs with the renal OC/H+(OC) exchanger results in the formation of a substrate-exchanger complex that has a comparatively low rate of turnover.

Long term monitoring of jaguars in the Cockscomb Basin Wildlife Sanctuary, Belize; Implications for camera trap studies of carnivores.

PubMed

Harmsen, Bart J; Foster, Rebecca J; Sanchez, Emma; Gutierrez-González, Carmina E; Silver, Scott C; Ostro, Linde E T; Kelly, Marcella J; Kay, Elma; Quigley, Howard

2017-01-01

In this study, we estimate life history parameters and abundance for a protected jaguar population using camera-trap data from a 14-year monitoring program (2002-2015) in Belize, Central America. We investigated the dynamics of this jaguar population using 3,075 detection events of 105 individual adult jaguars. Using robust design open population models, we estimated apparent survival and temporary emigration and investigated individual heterogeneity in detection rates across years. Survival probability was high and constant among the years for both sexes (φ = 0.78), and the maximum (conservative) age recorded was 14 years. Temporary emigration rate for the population was random, but constant through time at 0.20 per year. Detection probability varied between sexes, and among years and individuals. Heterogeneity in detection took the form of a dichotomy for males: those with consistently high detection rates, and those with low, sporadic detection rates, suggesting a relatively stable population of 'residents' consistently present and a fluctuating layer of 'transients'. Female detection was always low and sporadic. On average, twice as many males than females were detected per survey, and individual detection rates were significantly higher for males. We attribute sex-based differences in detection to biases resulting from social variation in trail-walking behaviour. The number of individual females detected increased when the survey period was extended from 3 months to a full year. Due to the low detection rates of females and the variable 'transient' male subpopulation, annual abundance estimates based on 3-month surveys had low precision. To estimate survival and monitor population changes in elusive, wide-ranging, low-density species, we recommend repeated surveys over multiple years; and suggest that continuous monitoring over multiple years yields even further insight into population dynamics of elusive predator populations.

Quantification of in vivo metabolic kinetics of hyperpolarized pyruvate in rat kidneys using dynamic 13C MRSI.

PubMed

Xu, Tao; Mayer, Dirk; Gu, Meng; Yen, Yi-Fen; Josan, Sonal; Tropp, James; Pfefferbaum, Adolf; Hurd, Ralph; Spielman, Daniel

2011-10-01

With signal-to-noise ratio enhancements on the order of 10,000-fold, hyperpolarized MRSI of metabolically active substrates allows the study of both the injected substrate and downstream metabolic products in vivo. Although hyperpolarized [1-(13)C]pyruvate, in particular, has been used to demonstrate metabolic activities in various animal models, robust quantification and metabolic modeling remain important areas of investigation. Enzyme saturation effects are routinely seen with commonly used doses of hyperpolarized [1-(13)C]pyruvate; however, most metrics proposed to date, including metabolite ratios, time-to-peak of metabolic products and single exchange rate constants, fail to capture these saturation effects. In addition, the widely used small-flip-angle excitation approach does not correctly model the inflow of fresh downstream metabolites generated proximal to the target slice, which is often a significant factor in vivo. In this work, we developed an efficient quantification framework employing a spiral-based dynamic spectroscopic imaging approach. The approach overcomes the aforementioned limitations and demonstrates that the in vivo (13)C labeling of lactate and alanine after a bolus injection of [1-(13)C]pyruvate is well approximated by saturatable kinetics, which can be mathematically modeled using a Michaelis-Menten-like formulation, with the resulting estimated apparent maximal reaction velocity V(max) and apparent Michaelis constant K(M) being unbiased with respect to critical experimental parameters, including the substrate dose, bolus shape and duration. Although the proposed saturatable model has a similar mathematical formulation to the original Michaelis-Menten kinetics, it is conceptually different. In this study, we focus on the (13)C labeling of lactate and alanine and do not differentiate the labeling mechanism (net flux or isotopic exchange) or the respective contribution of various factors (organ perfusion rate, substrate transport kinetics, enzyme activities and the size of the unlabeled lactate and alanine pools) to the labeling process. Copyright © 2011 John Wiley & Sons, Ltd.

Self-Consistency of the Lauritzen-Hoffman and Strobl Models of Polymer Crystallization Evaluated for Poly(epsilon-caprolactone) Fractions and Effect of Composition on the Phenomenon of Concurrent Crystallization in Polyethylene Blends

NASA Astrophysics Data System (ADS)

Sheth, Swapnil Suhas

Narrow molecular weight fractions of poly(epsilon-caprolactone) were successfully obtained using the successive precipitation fractionation technique with toluene/n-heptane as a solvent/nonsolvent pair. Calorimetric studies of the melting behavior of fractions that were crystallized either isothermally or under constant cooling rate conditions suggested that the isothermal crystallization of the samples should be used for a proper evaluation of the molecular weight dependence of the observed melting temperature and degree of crystallinity in PCL. The molecular weight and temperature dependence of the spherulitic growth rate of fractions was studied in the context of the Lauritzen-Hoffman two-phase model and the Strobl three-phase model of polymer crystallization. The zero-growth rate temperatures, determined from spherulitic growth rates using four different methods, are consistent with each other and increase with chain length. The concomitant increase in the apparent secondary nucleation constant was attributed to two factors. First, for longer chains there is an increase in the probability that crystalline stems belong to loose chain-folds, hence, an increase in fold surface free energy. It is speculated that the increase in loose folding and resulting decrease in crystallinity with increasing chain length are associated with the ester group registration requirement in PCL crystals. The second contribution to the apparent nucleation constant arises from chain friction associated with segmental transport across the melt/crystal interface. These factors were responsible for the much stronger chain length dependence of spherulitic growth rates at fixed undercooling observed here with PCL than previously reported for PE and PEO. In the case of PCL, the scaling exponent associated with the chain length dependence of spherulitic growth rates exceeds the upper theoretical bound of 2 predicted from the Brochard- DeGennes chain pullout model. Observation that zero-growth and equilibrium melting temperature values are identical with each other within the uncertainty of their determinations casts serious doubt on the validity of Strobl three-phase model. A novel method is proposed to determine the Porod constant necessary to extrapolate the small angle X-ray scattering intensity data to large scattering vectors. The one-dimensional correlation function determined using this Porod constant yielded the values of lamellar crystal thickness, which were similar to these estimated using the Hosemann-Bagchi Paracrystalline Lattice model. The temperature dependence of the lamellar crystal thickness was consistent with both LH and the Strobl model of polymer crystallization. However, in contrast to the predictions of Strobl's model, the value of the mesomorph-to-crystal equilibrium transition temperature was very close to the zero-growth temperature. Moreover, the lateral block sizes (obtained using wide angle X-ray diffraction) and the lamellar thicknesses were not found to be controlled by the mesomorph-to-crystal equilibrium transition temperature. Hence, we concluded that the crystallization of PCL is not mediated by a mesophase. Metallocene-catalyzed linear low-density (m-LLDPE with 3.4 mol% 1-octene) and conventional low-density (LDPE) polyethylene blends of different compositions were investigated for their melt-state miscibility and concurrent crystallization tendency. Differential scanning calorimetric studies and morphological studies using atomic force microscopy confirm that these blends are miscible in the melt-state for all compositions. LDPE chains are found to crystallize concurrently with m-LLDPE chains during cooling in the m-LLDPE crystallization temperature range. While the extent of concurrent crystallization was found to be optimal in .. .. iv blends with highest m-LLDPE content studied, strong evidence was uncovered for the existence of a saturation effect in the concurrent crystallization behavior. This observation leads us to suggest that co-crystallization, rather than mere concurrent crystallization, of LDPE with m- LLDPE can indeed take place. Matching of the respective sequence length distributions in LDPE and m-LLDPE is suggested to control the extent of co-crystallization.

Prediction of micropollutant elimination during ozonation of a hospital wastewater effluent.

PubMed

Lee, Yunho; Kovalova, Lubomira; McArdell, Christa S; von Gunten, Urs

2014-11-01

Determining optimal ozone doses for organic micropollutant elimination during wastewater ozonation is challenged by the presence of a large number of structurally diverse micropollutants for varying wastewater matrice compositions. A chemical kinetics approach based on ozone and hydroxyl radical (·OH) rate constant and measurements of ozone and ·OH exposures is proposed to predict the micropollutant elimination efficiency. To further test and validate the chemical kinetics approach, the elimination efficiency of 25 micropollutants present in a hospital wastewater effluent from a pilot-scale membrane bioreactor (MBR) were determined at pH 7.0 and 8.5 in bench-scale experiments with ozone alone and ozone combined with H2O2 as a function of DOC-normalized specific ozone doses (gO3/gDOC). Furthermore, ozone and ·OH exposures, ·OH yields, and ·OH consumption rates were determined. Consistent eliminations as a function of gO3/gDOC were observed for micropollutants with similar ozone and ·OH rate constants. They could be classified into five groups having characteristic elimination patterns. By increasing the pH from 7.0 to 8.5, the elimination levels increased for the amine-containing micropollutants due to the increased apparent second-order ozone rate constants while decreased for most micropollutants due to the diminished ozone or ·OH exposures. Increased ·OH quenching by effluent organic matter and carbonate with increasing pH was responsible for the lower ·OH exposures. Upon H2O2 addition, the elimination levels of the micropollutants slightly increased at pH 7 (<8%) while decreased considerably at pH 8.5 (up to 31%). The elimination efficiencies of the selected micropollutants could be predicted based on their ozone and ·OH rate constants (predicted or taken from literature) and the determined ozone and ·OH exposures. Reasonable agreements between the measured and predicted elimination levels were found, demonstrating that the proposed chemical kinetics method can be used for a generalized prediction of micropollutant elimination during wastewater ozonation. Out of 67 analyzed micropollutants, 56 were present in the tested hospital wastewater effluent. Two-thirds of the present micropollutants were found to be ozone-reactive and efficiently eliminated at low ozone doses (e.g., >80% for gO3/gDOC = 0.5). Copyright © 2014 Elsevier Ltd. All rights reserved.

Buckling of Thermoviscoelastic Structures Under Temporal and Spatial Temperature Variations

NASA Technical Reports Server (NTRS)

Tsuyuki, Richard; Knauss, Wolfgang G.

1992-01-01

The problem of lateral instability of a viscoelastic in-plane loaded structure is considered in terms of thermorheolgically simple materials. As an example of a generally in-plane loaded structure, we examine the simple column under axial load: Both cyclic loading is considered (with constant or in-phase variable temperature excursions) as well as the case of constant load in the presence of thermal gradients through the thickness of the structure. The latter case involves a continuous movement of the neutral axis from the center to the colder side and then back to the center. In both cases, temperature has a very strong effect on the instability evolution, and under in-phase thermal cycling the critical loads are reduced compared to those at constant temperatures. The primary effect of thermal gradients beyond that of thermally-induced rate accelerations is occasioned by the generation of an "initial imperfection" or "structural bowing." Because the coefficient of thermal expansion tends to be large for many polymeric materials, it it may be necessary to take special care in lay-up design of composite structures intended for use under compressive loads in high-temperature applications. Finally, the implications for the temperature sensitivities of composites to micro-instability (fiber crimping) are also apparent from the results delineated here.

Movements of labelled sodium ions in isolated rat superior cervical ganglia

PubMed Central

Brown, D. A.; Scholfield, C. N.

1974-01-01

1. Isolated rat superior cervical ganglia were incubated in Krebs solution containing 24Na and carbachol for 4 min at 25° C. They were then washed at 3° C for 15 min to remove extracellular 24Na and the efflux of residual intracellular 24Na stimulated by warming to 25° C. 2. During the 15 min wash at 3° C desaturation curves became exponential with a rate constant of 0·012 ± 0·001 min-1 (n = 24). This was assumed to represent loss of intracellular 24Na, and initial uptake of 24Na was calculated therefrom by back-extrapolation to zero wash-time. After 4 min in 24Na + 180 μM carbachol intracellular [24Na] so calculated was 61·6 ± 3·1 mM (n = 18), representing 83% labelling of intracellular Na. In the absence of carbachol intracellular [24Na] was 10·0 ± 0·5 mM, representing 49% labelling. Extracellular Na was labelled by > 90% after 4 min in 24Na. The apparent rate constant for washout of extracellular 24Na was 0·6 min-1 at 3° C and 0·95 min-1 at 25° C. 3. The loss of the residual intracellular 24Na during temperature stimulation was interpreted quantitatively in terms of an exponential decline of the bulk of intracellular 24Na with an extrusion rate constant of 0·39 ± 0·1 min-1 (n = 18), efflux being delayed by passage through the extracellular space with an effective rate constant of 0·8-1·2 min-1. 4. The peak rate constant (kC) for the desaturation curve at 25° C was 0·35 ± 0·01 min-1. An Arrhenius plot of log kC/T° K-1 yielded a two-stage linear regression with a transition at 20° C. Activation energies of 8 and 31 kcal. mole-1 were calculated above and below this transition respectively. 5. Omission of K from the 25° C temperature-stimulating solution reduced kC by 62%. The K-sensitive component of extrusion rate constant was a hyperbolic function of [K]e with half-saturation at 5·6 mM-[K]e and maximum kC of 0·58 min-1. 6. Cyanide (2 mM), 2,4-dinitrophenol (1 mM) and ouabain (1·4 mM) reduced kC by 50-90%. The half-maximally inhibiting concentration of ouabain was about 60 μM. 7. Substitution of sucrose, Li or choline for external Na did not reduce the extrusion rate of 24Na in either 6 mM-[K]e or 0 mM-[K]e. Li stimulated 24Na extrusion in Na-free, K-free solution. 8. The properties of the ganglionic Na pump deduced from rates of temperature-stimulated 24Na extrusion accord with the view that the ganglion hyperpolarization observed after Na loading by exposure to nicotinic depolarizing agents results from electrogenic Na extrusion. A comparable hyperpolarization is observed after temperature stimulation following Na loading. PMID:4455816

Coupled alkali feldspar dissolution and secondary mineral precipitation in batch systems: 4. Numerical modeling of kinetic reaction paths

NASA Astrophysics Data System (ADS)

Zhu, Chen; Lu, Peng; Zheng, Zuoping; Ganor, Jiwchar

2010-07-01

This paper explores how dissolution and precipitation reactions are coupled in batch reactor experimental systems at elevated temperatures. This is the fourth paper in our series of "Coupled Alkali Feldspar Dissolution and Secondary Mineral Precipitation in Batch Systems". In our third paper, we demonstrated via speciation-solubility modeling that partial equilibrium between secondary minerals and aqueous solutions was not attained in feldspar hydrolysis batch reactors at 90-300 °C and that a strong coupling between dissolution and precipitation reactions follows as a consequence of the slower precipitation of secondary minerals ( Zhu and Lu, 2009). Here, we develop this concept further by using numerical reaction path models to elucidate how the dissolution and precipitation reactions are coupled. Modeling results show that a quasi-steady state was reached. At the quasi-steady state, dissolution reactions proceeded at rates that are orders of magnitude slower than the rates measured at far from equilibrium. The quasi-steady state is determined by the relative rate constants, and strongly influenced by the function of Gibbs free energy of reaction ( ΔG) in the rate laws. To explore the potential effects of fluid flow rates on the coupling of reactions, we extrapolate a batch system ( Ganor et al., 2007) to open systems and simulated one-dimensional reactive mass transport for oligoclase dissolution and kaolinite precipitation in homogeneous porous media. Different steady states were achieved at different locations along the one-dimensional domain. The time-space distribution and saturation indices (SI) at the steady states were a function of flow rates for a given kinetic model. Regardless of the differences in SI, the ratio between oligoclase dissolution rates and kaolinite precipitation rates remained 1.626, as in the batch system case ( Ganor et al., 2007). Therefore, our simulation results demonstrated coupling among dissolution, precipitation, and flow rates. Results reported in this communication lend support to our hypothesis that slow secondary mineral precipitation explains part of the well-known apparent discrepancy between lab measured and field estimated feldspar dissolution rates ( Zhu et al., 2004). Here we show how the slow secondary mineral precipitation provides a regulator to explain why the systems are held close to equilibrium and show how the most often-quoted "near equilibrium" explanation for an apparent field-lab discrepancy can work quantitatively. The substantiated hypothesis now offers the promise of reconciling part of the apparent field-lab discrepancy.

Na(+)-dependent transport of taurine is found only on the abluminal membrane of the blood-brain barrier.

PubMed

Rasgado-Flores, Hector; Mokashi, Ashwini; Hawkins, Richard A

2012-01-01

Luminal and abluminal plasma membranes were isolated from bovine brain microvessels and used to identify and characterize Na(+)-dependent and facilitative taurine transport. The calculated transmembrane potential was -59 mV at time 0; external Na(+) (or choline under putative zero-trans conditions) was 126 mM (T=25 °C). The apparent affinity constants of the taurine transporters were determined over a range of taurine concentrations from 0.24 μM to 11.4 μM. Abluminal membranes had both Na(+)-dependent taurine transport as well as facilitative transport while luminal membranes only had facilitative transport. The apparent K(m) for facilitative and Na(+)-dependent taurine transport were 0.06±0.02 μM and 0.7±0.1 μM, respectively. The Na(+)-dependent transport of taurine was voltage dependent over the range of voltages studied (-25 to -101 mV). The transport was over 5 times greater at -101 mV compared to when V(m) was -25 mV. The sensitivity to external osmolality of Na(+)-dependent transport was studied over a range of osmolalities (229 to 398 mOsm/kg H(2)O) using mannitol as the osmotic agent to adjust the osmolality. For these experiments the concentration of Na(+) was maintained constant at 50mM, and the calculated transmembrane potential was -59 mV. The Na(+)-dependent transport system was sensitive to osmolality with the greatest rate observed at 229 mOsm/kg H(2)O. Copyright © 2011 Elsevier Inc. All rights reserved.

The rate of sulfide oxidation by δMnO 2 in seawater

NASA Astrophysics Data System (ADS)

Yao, Wensheng; Millero, Frank J.

1993-07-01

The rate of oxidation of hydrogen sulfide by manganese dioxide in seawater was determined as a function of pH (2.0-9.0), temperature (5-45°C), and ionic strength (0-4 M). The overall rate constant, k, in seawater at pH = 8.17 was found to be first order with respect to both sulfide and manganese dioxide: - d[H 2S] T/dt = k[H 2S] τ[MnO 2] . The rate constant, k, for seawater (S = 35.8, pH = 8.17) at 25°C was found to be 436 M -1 min -1, or 0.0244 m -2 1 min -1 when [MnO 2] is expressed in surface area (m 2/L). The energies of activation were found to be 14 ± 1 KJ mol -1 and 10 ± 1 KJ mol -1, respectively, for pH = 8.2 and pH = 5.0 in seawater (S = 35). The rate increased from pH 2.0 to a maximum at a pH of about 5.0 and decreased at higher pH. This pH dependence was attributed to formation of a surface complex between >MnO - and H 2S. As the concentration of HS - increases above pH = 5 the rate of the reaction decreases. The rate of sulfide oxidation by MnO 2 is not strongly dependent on ionic strength. The rates in 0.57 M NaCl were found to be slightly higher than the rates in seawater. Measurements made in solutions of the major sea salts indicated that Ca 2+ and Mg 2+ caused the rates to decrease, apparently by absorbing on the surface of manganese dioxide. Measurements made in artificial seawater (Na +, Mg 2+, Ca 2+, Cl -, and SO 2-4) were found to be in good agreement with the measurements in actual seawater. Phosphate was found to inhibit the reaction significantly.

A generalized law for brittle deformation of Westerly granite

USGS Publications Warehouse

Lockner, D.A.

1998-01-01

A semiempirical constitutive law is presented for the brittle deformation of intact Westerly granite. The law can be extended to larger displacements, dominated by localized deformation, by including a displacement-weakening break-down region terminating in a frictional sliding regime often described by a rate- and state-dependent constitutive law. The intact deformation law, based on an Arrhenius type rate equation, relates inelastic strain rate to confining pressure Pc, differential stress ????, inelastic strain ??i, and temperature T. The basic form of the law for deformation prior to fault nucleation is In ????i = c - (E*/RT) + (????/a??o)sin-??(???? i/2??o) where ??o and ??o are normalization constants (dependent on confining pressure), a is rate sensitivity of stress, and ?? is a shape parameter. At room temperature, eight experimentally determined coefficients are needed to fully describe the stress-strain-strain rate response for Westerly granite from initial loading to failure. Temperature dependence requires apparent activation energy (E* ??? 90 kJ/mol) and one additional experimentally determined coefficient. The similarity between the prefailure constitutive law for intact rock and the rate- and state-dependent friction laws for frictional sliding on fracture surfaces suggests a close connection between these brittle phenomena.

A new macrocyclic terbium(III) complex for use in RNA footprinting experiments

PubMed Central

Belousoff, Matthew J.; Ung, Phuc; Forsyth, Craig M.; Tor, Yitzhak; Spiccia, Leone; Graham, Bim

2009-01-01

Reaction of terbium triflate with a heptadentate ligand derivative of cyclen, L1 = 2-[7-ethyl-4,10-bis(isopropylcarbamoylmethyl)-1,4,7,10-tetraazacyclododec-1-yl]-N-isopropylacetamide, produced a new synthetic ribonuclease, [Tb(L1)(OTf)(OH2)](OTf)2·MeCN (C1). X-ray crystal structure analysis indicates that the terbium(III) centre in C1 is 9-coordinate, with a capped square-antiprism geometry. Whilst the terbium(III) center is tightly bound by the L1 ligand, two of the coordination sites are occupied by labile water and triflate ligands. In water, the triflate ligand is likely to be displaced, forming [Tb(L1)(OH2)2]3+, which is able to effectively promote RNA cleavage. This complex greatly accelerates the rate of intramolecular transesterification of an activated model RNA phosphodiester, uridine-3′-p-nitrophenylphosphate (UpNP), with kobs = 5.5(1) × 10-2 s-1 at 21°C and pH 7.5, corresponding to an apparent second-order rate constant of 277(5) M-1s-1. By contrast, the analogous complex of an octadentate derivative of cyclen featuring only a single labile coordination site, [Tb(L2)(OH2)](OTf)3 (C2), where L2 = 2-[4,7,10-tris(isopropylcarbamoylmethyl)-1,4,7,10-tetraazacyclododec-1-yl]-N-isopropyl-acetamide, is inactive. [Tb(L1)(OH2)2]3+ is also capable of hydrolyzing short transcripts of the HIV-1 transactivation response (TAR) element, HIV-1 dimerization initiation site (DIS) and ribosomal A-site, as well as formyl methionine transfer RNA (tRNAfMet), albeit at a considerably slower rate than UpNP transesterification (kobs = 2.78(8) × 10-5 M-1s-1 for TAR cleavage at 37°C, pH 6.5, corresponding to an apparent second-order rate constant of 0.56(2) M-1s-1). Cleavage is concentrated at the single-stranded “bulge” regions of these RNA motifs. Exploiting this selectivity, [Tb(L1)(OH2)23+ was successfully employed in footprinting experiments, in which binding of the Tat peptide and neomycin B to the bulge region of the TAR stem-loop was confirmed. PMID:19119812

Gas phase chemistry in gallium nitride CVD: Theoretical determination of the Arrhenius parameters for the first Ga-C bond homolysis of trimethylgallium.

PubMed

Schmid, Rochus; Basting, Daniel

2005-03-24

Experimental evidence suggests that the energy of activation for the first homolytic Ga-C bond fission of GaMe3 of Ea = 249 kJ/mol, measured by Jacko and Price in a hot-wall tube reactor, is affected by surface catalytic effects. In this contribution, the rate constant for this crucial step in the gas-phase pyrolysis of GaMe3 has been calculated by variational transition state theory. By a basis set extrapolation on the MP2/cc-pVXZ level and a correlation correction from CCSD(T)/cc-pVDZ level, a theoretical "best estimate" for the bond energy of Delta H(289K) = 327.2 kJ/mol was derived. For the VTST calculation on the B3LYP/cc-pVDZ level, the energies were corrected to reproduce this bond energy. Partition functions of the transitional modes were approximated by a hindered rotor approximation to be valid along the whole reaction coordinate defined by the Ga-C bond length. On the basis of the canonical transition state theory, reaction rates were determined using the maxima of the free energy Delta G++. An Arrhenius-type rate law was fitted to these rate constants, yielding an apparent energy of activation of Ea = 316.7 kJ/mol. The preexponential factor A = 3.13 x 10(16) 1/s is an order of magnitude larger than the experimental results because of a larger release of entropy at the transition state as compared to that of the unknown surface catalyzed mechanism.

Voltage gating by molecular subunits of Na+ and K+ ion channels: higher-dimensional cubic kinetics, rate constants, and temperature

PubMed Central

2015-01-01

The structural similarity between the primary molecules of voltage-gated Na and K channels (alpha subunits) and activation gating in the Hodgkin-Huxley model is brought into full agreement by increasing the model's sodium kinetics to fourth order (m3 → m4). Both structures then virtually imply activation gating by four independent subprocesses acting in parallel. The kinetics coalesce in four-dimensional (4D) cubic diagrams (16 states, 32 reversible transitions) that show the structure to be highly failure resistant against significant partial loss of gating function. Rate constants, as fitted in phase plot data of retinal ganglion cell excitation, reflect the molecular nature of the gating transitions. Additional dimensions (6D cubic diagrams) accommodate kinetically coupled sodium inactivation and gating processes associated with beta subunits. The gating transitions of coupled sodium inactivation appear to be thermodynamically irreversible; response to dielectric surface charges (capacitive displacement) provides a potential energy source for those transitions and yields highly energy-efficient excitation. A comparison of temperature responses of the squid giant axon (apparently Arrhenius) and mammalian channel gating yields kinetic Q10 = 2.2 for alpha unit gating, whose transitions are rate-limiting at mammalian temperatures; beta unit kinetic Q10 = 14 reproduces the observed non-Arrhenius deviation of mammalian gating at low temperatures; the Q10 of sodium inactivation gating matches the rate-limiting component of activation gating at all temperatures. The model kinetics reproduce the physiologically large frequency range for repetitive firing in ganglion cells and the physiologically observed strong temperature dependence of recovery from inactivation. PMID:25867741

Kinetic sorption of contaminants of emerging concern by a palygorskite-montmorillonite filter medium.

PubMed

Berhane, Tedros M; Levy, Jonathan; Krekeler, Mark P S; Danielson, Neil D

2017-06-01

Kinetic sorption of bisphenol A (BPA), carbamazepine (CMZ) and ciprofloxacin (CIP) by three palygorskite-montmorillonite (Pal-Mt) granule sizes was studied. For BPA, CMZ and CIP, apparent sorption equilibrium was reached within about 3, 5 and 16 h, respectively. The highest and the lowest sorption capacities were by the small and the large granule sizes, respectively. Experimental results were compared to various sorption kinetics models to gain insights regarding the sorption processes and achieve a predictive capacity. The pseudo-second order (PSO) and the Elovich models performed the best while the pseudo-first order (PFO) model was only adequate for CMZ. The intraparticle-diffusion (IPD) model showed a two-step linear plot of BPA, CMZ and CIP sorption versus square root of time that was indicative of surface-sorption followed by IPD as a rate-limiting process before equilibrium was reached. Using the pseudo-first order (PFO) and the pseudo-second order (PSO) rate constants combined with previously-established Langmuir equilibrium sorption models, the kinetic sorption (k a ) and desorption (k d ) Langmuir kinetic rate constants were theoretically calculated for BPA and CIP. Kinetic sorption was then simulated using these theoretically calculated k a and k d values, and the simulations were compared to the observed behavior. The simulations fit the observed sorbed concentrations better during the early part of the experiments; the observed sorption during later times occurred more slowly than expected, supporting the hypothesis that IPD becomes a rate-limiting process during the course of the experiment. Copyright © 2017 Elsevier Ltd. All rights reserved.

New mixed ligand palladium(II) complexes based on the antiepileptic drug sodium valproate and bioactive nitrogen-donor ligands: Synthesis, structural characterization, binding interactions with DNA and BSA, in vitro cytotoxicity studies and DFT calculations

NASA Astrophysics Data System (ADS)

Tabrizi, Leila; Chiniforoshan, Hossein; Tavakol, Hossein

2015-04-01

The complexes [Pd(valp)2(imidazole)2] (1), [Pd(valp)2(pyrazine)2] (2) (valp is sodium valproate) have been synthesized and characterized using IR, 1H NMR, 13C{1H} NMR and UV-Vis spectrometry. The interaction of complexes with CT-DNA has been investigated using spectroscopic tools and viscosity measurement. In each case, the association constant (Kb) was deduced from the absorption spectral study and the number of binding sites (n) and the binding constant (K) were calculated from relevant fluorescence quenching data. As a result, a non-covalent interaction between the metal complex and DNA was suggested, which could be assigned to an intercalative binding. In addition, the interaction of 1 and 2 was ventured with bovine serum albumin (BSA) with the help of absorption and fluorescence spectroscopy measurements. Through these techniques, the apparent association constant (Kapp) and the binding constant (K) could be calculated for each complex. Evaluation of cytotoxic activity of the complexes against four different cancer cell lines proved that the complexes exhibited cytotoxic specificity and significant cancer cell inhibitory rate. Moreover, density functional theory (DFT) calculations were employed to provide more evidence about the observed data. The majority of trans isomers were supported not only by energies, but also by the similarity of its calculated IR frequencies, UV adsorptions and NMR chemical shifts to the experimental values.

Zooxanthellar symbiosis in planula larvae of the coral Pocillopora damicornis.

PubMed

Gaither, Michelle R; Rowan, Rob

2010-04-30

We characterized the planular-zooxanthellae symbiosis of the coral Pocillopora damicornis using criteria that are familiar in studies on corals. Similar to adult corals, planulae exhibited photoacclimation, as changes in symbiont chlorophyll a (chl a); changes in the light-saturation constant for photosynthesis (I(k)); and, at insufficient light, fewer zooxanthellae, decreased respiration, increased weight loss, and increased sensitivity to photoinhibition. Numbers of zooxanthellae in newly-released planulae varied by at least three-fold within broods. Planulae with low versus high numbers of zooxanthellae (termed pale versus dark planulae, respectively) did not differ in symbiont chl-a content, I(k), or biomass-specific rate of dark respiration. Pale planulae had lower rates of photosynthesis, but this difference vanished after three weeks, when zooxanthellar numbers increased by 225% in pale planulae and by 31% in dark planulae. Numbers of zooxanthellae also increased significantly in planulae cultured in ammonium-enriched seawater; ammonium also apparently prevented weight loss and induced settlement. Approximately 70% of photosynthetically-fixed carbon (labeled using (14)C) apparently was translocated from the zooxanthellae to their host. A comparison of planulae cultured at 0.3% versus 11% sunlight suggested that photosynthesis provided ~ 31% of the energy utilized by the latter. Overall, we conclude that the physiology of symbiosis in planulae of P. damicornis is broadly similar to symbiosis physiology in adult corals.

Microbial metabolic activity in soil as measured by dehydrogenase determinations

NASA Technical Reports Server (NTRS)

Casida, L. E., Jr.

1977-01-01

The dehydrogenase technique for measuring the metabolic activity of microorganisms in soil was modified to use a 6-h, 37 C incubation with either glucose or yeast extract as the electron-donating substrate. The rate of formazan production remained constant during this time interval, and cellular multiplication apparently did not occur. The technique was used to follow changes in the overall metabolic activities of microorganisms in soil undergoing incubation with a limiting concentration of added nutrient. The sequence of events was similar to that obtained by using the Warburg respirometer to measure O2 consumption. However, the major peaks of activity occurred earlier with the respirometer. This possibly is due to the lack of atmospheric CO2 during the O2 consumption measurements.

Aeronomical determinations of the quantum yields of O (1S) and O (1D) from dissociative recombination of O2(+)

NASA Technical Reports Server (NTRS)

Yee, Jeng-Hwa; Abreu, Vincent J.; Colwell, William B.

1989-01-01

Data from the visible-airglow experiment on the Atmosphere Explorer-E satellite have been used to determine the quantum yields of O (1S) and O (1D) from the dissociative recombination of O2(+) based on a constant total recombination rate from each vibrational level. A range of values between 0.05 and 0.18 has been obtained for the quantum yield of O (1S) and shows a positive correlation with the extent of the vibrational excitation of O2(+). The quantum yield of O (1D) has been measured to be 0.9 + or - 0.2, with no apparent dependence on the vibrational distribution of O2(+).

Kinetic Modeling of a Heterogeneous Fenton Oxidative Treatment of Petroleum Refining Wastewater

PubMed Central

Basheer Hasan, Diya'uddeen; Abdul Raman, Abdul Aziz; Wan Daud, Wan Mohd Ashri

2014-01-01

The mineralisation kinetics of petroleum refinery effluent (PRE) by Fenton oxidation were evaluated. Within the ambit of the experimental data generated, first-order kinetic model (FKM), generalised lumped kinetic model (GLKM), and generalized kinetic model (GKM) were tested. The obtained apparent kinetic rate constants for the initial oxidation step (k 2′), their final oxidation step (k 1′), and the direct conversion to endproducts step (k 3′) were 10.12, 3.78, and 0.24 min−1 for GKM; 0.98, 0.98, and nil min−1 for GLKM; and nil, nil, and >0.005 min−1 for FKM. The findings showed that GKM is superior in estimating the mineralization kinetics. PMID:24592152

Chromatographic determination of itopride hydrochloride in the presence of its degradation products.

PubMed

Kaul, Neeraj; Agrawal, Himani; Maske, Pravin; Rao, Janhavi Ramchandra; Mahadik, Kakasaheb Ramoo; Kadam, Shivajirao S

2005-08-01

Two sensitive and reproducible methods are described for the quantitative determination of itopride hydrochloride (IH) in the presence of its degradation products. The first method is based on HPLC separation on a reversed phase Kromasil column [C18 (5-microm, 25 cm x 4.6 mm, ID)] at ambient temperature using a mobile phase consisting of methanol and water (70:30, v/v) adjusted to pH 4.0 with orthophosphoric acid with UV detection at 258 nm. The flow rate was 1.0 mL per min with an average operating pressure of 180 kg/cm2. The second method is based on HPTLC separation on silica gel 60 F254 using toluene:methanol:chloroform:10% ammonia (5.0:3.0:6.0:0.1, v/v/v/v) as mobile phase at 270 nm. The analysis of variance (ANOVA) and Student's t-test were applied to correlate the results of IH determination in dosage form by means of HPLC and HPTLC methods. The drug was subjected to acid and alkali hydrolysis, oxidation, dry heat, wet heat treatment, UV, and photodegradation. The proposed HPLC method was utilized to investigate the kinetics of the acidic, alkaline, and oxidative degradation processes at different temperatures and the apparent pseudo-first-order rate constant, half-life, and activation energy were calculated. In addition the pH-rate profile of degradation of IH in constant ionic strength buffer solutions in the pH range 2-11 was studied.

Quantification of rapid environmental redox processes with quick-scanning x-ray absorption spectroscopy (Q-XAS)

PubMed Central

Ginder-Vogel, Matthew; Landrot, Gautier; Fischel, Jason S.; Sparks, Donald L.

2009-01-01

Quantification of the initial rates of environmental reactions at the mineral/water interface is a fundamental prerequisite to determining reaction mechanisms and contaminant transport modeling and predicting environmental risk. Until recently, experimental techniques with adequate time resolution and elemental sensitivity to measure initial rates of the wide variety of environmental reactions were quite limited. Techniques such as electron paramagnetic resonance and Fourier transform infrared spectroscopies suffer from limited elemental specificity and poor sensitivity to inorganic elements, respectively. Ex situ analysis of batch and stirred-flow systems provides high elemental sensitivity; however, their time resolution is inadequate to characterize rapid environmental reactions. Here we apply quick-scanning x-ray absorption spectroscopy (Q-XAS), at sub-second time-scales, to measure the initial oxidation rate of As(III) to As(V) by hydrous manganese(IV) oxide. Using Q-XAS, As(III) and As(V) concentrations were determined every 0.98 s in batch reactions. The initial apparent As(III) depletion rate constants (t < 30 s) measured with Q-XAS are nearly twice as large as rate constants measured with traditional analytical techniques. Our results demonstrate the importance of developing analytical techniques capable of analyzing environmental reactions on the same time scale as they occur. Given the high sensitivity, elemental specificity, and time resolution of Q-XAS, it has many potential applications. They could include measuring not only redox reactions but also dissolution/precipitation reactions, such as the formation and/or reductive dissolution of Fe(III) (hydr)oxides, solid-phase transformations (i.e., formation of layered-double hydroxide minerals), or almost any other reaction occurring in aqueous media that can be measured using x-ray absorption spectroscopy. PMID:19805269

Physical properties of ice cream containing milk protein concentrates.

PubMed

Alvarez, V B; Wolters, C L; Vodovotz, Y; Ji, T

2005-03-01

Two milk protein concentrates (MPC, 56 and 85%) were studied as substitutes for 20 and 50% of the protein content in ice cream mix. The basic mix formula had 12% fat, 11% nonfat milk solids, 15% sweetener, and 0.3% stabilizer/emulsifier blend. Protein levels remained constant, and total solids were compensated for in MPC mixes by the addition of polydextrose. Physical properties investigated included apparent viscosity, fat globule size, melting rate, shape retention, and freezing behavior using differential scanning calorimetry. Milk protein concentrate formulations had higher mix viscosity, larger amount of fat destabilization, narrower ice melting curves, and greater shape retention compared with the control. Milk protein concentrates did not offer significant modifications of ice cream physical properties on a constant protein basis when substituted for up to 50% of the protein supplied by nonfat dry milk. Milk protein concentrates may offer ice cream manufacturers an alternative source of milk solids non-fat, especially in mixes reduced in lactose or fat, where higher milk solids nonfat are needed to compensate other losses of total solids.

Population Demographic History Can Cause the Appearance of Recombination Hotspots

PubMed Central

Johnston, Henry R.; Cutler, David J.

2012-01-01

Although the prevailing view among geneticists suggests that recombination hotspots exist ubiquitously across the human genome, there is only limited experimental evidence from a few genomic regions to support the generality of this claim. A small number of true recombination hotspots are well supported experimentally, but the vast majority of hotspots have been identified on the basis of population genetic inferences from the patterns of linkage disequilibrium (LD) seen in the human population. These inferences are made assuming a particular model of human history, and one of the assumptions of that model is that the effective population size of humans has remained constant throughout our history. Our results show that relaxation of the constant population size assumption can create LD and variation patterns that are qualitatively and quantitatively similar to human populations without any need to invoke localized hotspots of recombination. In other words, apparent recombination hotspots could be an artifact of variable population size over time. Several lines of evidence suggest that the vast majority of hotspots identified on the basis of LD information are unlikely to have elevated recombination rates. PMID:22560089

A new nitrilase-producing strain named Rhodobacter sphaeroides LHS-305: biocatalytic characterization and substrate specificity.

PubMed

Yang, Chunsheng; Wang, Xuedong; Wei, Dongzhi

2011-12-01

The characteristics of the new nitrilase-producing strain Rhodobacter sphaeroides LHS-305 were investigated. By investigating several parameters influencing nitrilase production, the specific cell activity was ultimately increased from 24.5 to 75.0 μmol g(-1) min(-1), and hereinto, the choice of inducer proved the most important factor. The aromatic nitriles (such as 3-cyanopyridine and benzonitrile) were found to be the most favorable substrates of the nitrilase by analyzing the substrate spectrum. It was speculated that the unsaturated carbon atom attached to the cyano group was crucial for this type of nitrilase. The value of apparent K (m), substrate inhibition constant, and product inhibition constant of the nitrilase against 3-cyanopyridine were 4.5 × 10(-2), 29.2, and 8.6 × 10(-3) mol L(-1), respectively. When applied in nicotinic acid preparation, the nitrilase is able to hydrolyze 200 mmol L(-1) 3-cyanopyridine with 93% conversion rate in 13 h by 6.1 g L(-1) cells (dry cell weight).

Relative Propensities of Cytochrome c Oxidase and Cobalt Corrins for Reaction with Cyanide and Oxygen: Implications for Amelioration of Cyanide Toxicity.

PubMed

Yuan, Quan; Pearce, Linda L; Peterson, Jim

2017-12-18

In aqueous media at neutral pH, the binding of two cyanide molecules per cobinamide can be described by two formation constants, K f1 = 1.1 (±0.6) × 10 5 M -1 and K f2 = 8.5 (±0.1) × 10 4 M -1 , or an overall cyanide binding constant of ∼1 × 10 10 M -2 . In comparison, the cyanide binding constants for cobalamin and a fully oxidized form of cytochrome c oxidase, each binding a single cyanide anion, were found to be 7.9 (±0.5) × 10 4 M -1 and 1.6 (±0.2) × 10 7 M -1 , respectively. An examination of the cyanide-binding properties of cobinamide at neutral pH by stopped-flow spectrophotometry revealed two kinetic phases, rapid and slow, with apparent second-order rate constants of 3.2 (±0.5) × 10 3 M -1 s -1 and 45 (±1) M -1 s -1 , respectively. Under the same conditions, cobalamin exhibited a single slow cyanide-binding kinetic phase with a second-order rate constant of 35 (±1) M -1 s -1 . All three of these processes are significantly slower than the rate at which cyanide is bound by complex IV during enzyme turnover (>10 6 M -1 s -1 ). Overall, it can be understood from these findings why cobinamide is a measurably better cyanide scavenger than cobalamin, but it is unclear how either cobalt corrin can be antidotal toward cyanide intoxication as neither compound, by itself, appears able to out-compete cytochrome c oxidase for available cyanide. Furthermore, it has also been possible to unequivocally show in head-to-head comparison assays that the enzyme does indeed have greater affinity for cyanide than both cobalamin and cobinamide. A plausible resolution of the paradox that both cobalamin and cobinamide clearly are antidotal toward cyanide intoxication, involving the endogenous auxiliary agent nitric oxide, is suggested. Additionally, the catalytic consumption of oxygen by the cobalt corrins is demonstrated and, in the case of cobinamide, the involvement of cytochrome c when present. Particularly in the case of cobinamide, these oxygen-dependent reactions could potentially lead to erroneous assessment of the ability of the cyanide scavenger to restore the activity of cyanide-inhibited cytochrome c oxidase.

Kinetics of the solid-state carbothermic reduction of wessel manganese ores

NASA Astrophysics Data System (ADS)

Akdogan, Guven; Eric, R. Hurman

1995-02-01

Reduction of manganese ores from the Wessel mine of South Africa has been investigated in the temperature range 1100 °C to 1350 °C with pure graphite as the reductant under argon atmosphere. The rate and degree of reduction were found to increase with increasing temperature and decreasing particle sizes of both the ore and the graphite. The reduction was found to occur in two stages: (1) The first stage includes the rapid reduction of higher oxides of manganese and iron to MnO and FeO. The rate control appears to be mixed, both inward diffusion of CO and outward diffusion of CO2 across the porous product layer, and the reaction of carbon monoxide on the pore walls of the oxide phase play important roles. The values of effective CO-CO2 diffusivities generated by the mathematical model are in the range from 2.15 x 10-5 to 6.17 X 10-5 cm2.s-1 for different ores at 1300 °C. Apparent activation energies range from 81. 3 to 94.6 kJ/kg/mol. (2) The second stage is slower during which MnO and FeO are reduced to mixed carbide of iron and manganese. The chemical reaction between the manganous oxide and carbon dissolved in the metal phase or metal carbide seems to be the rate-controlling process The rate constant of chemical reaction between MnO and carbide on the surface of the impervious core was found to lie in the range from 1.53 x 10-8 to 1.32 x 10-7 mol . s-1 . cm-2. Apparent activation energies calculated are in the range from 102.1 to 141.7 kJ/kg/mol.

A simple but powerful theory of the moon illusion.

PubMed

Baird, J C; Wagner, M; Fuld, K

1990-08-01

Modification of Restle's theory (1970) explains the moon illusion and related phenomena on the basis of three principles: (1) The apparent sizes of objects are their perceived visual angles. (2) The apparent size of the moon is determined by the ratio of the angular extent of the moon relative to the extents subtended by objects composing the surrounding context, such as the sky and things on the ground. (3) The visual extents subtended by common objects of a constant physical size decrease systematically with increasing distance from the observer. Further development of this theory requires specification of both the components of the surrounding context and their relative importance in determining the apparent size and distance of the moon.

Modelling of the acid-base properties of natural and synthetic adsorbent materials used for heavy metal removal from aqueous solutions.

PubMed

Pagnanelli, Francesca; Vegliò, Francesco; Toro, Luigi

2004-02-01

In this paper a comparison about kinetic behaviour, acid-base properties and copper removal capacities was carried out between two different adsorbent materials used for heavy metal removal from aqueous solutions: an aminodiacetic chelating resin as commercial product (Lewatit TP207) and a lyophilised bacterial biomass of Sphaerotilus natans. The acid-base properties of a S. natans cell suspension were well described by simplified mechanistic models without electrostatic corrections considering two kinds of weakly acidic active sites. In particular the introduction of two-peak distribution function for the proton affinity constants allows a better representation of the experimental data reproducing the site heterogeneity. A priori knowledge about resin functional groups (aminodiacetic groups) is the base for preliminary simulations of titration curve assuming a Donnan gel structure for the resin phase considered as a concentrated aqueous solution of aminodiacetic acid (ADA). Departures from experimental and simulated data can be interpreted by considering the heterogeneity of the functional groups and the effect of ionic concentration in the resin phase. Two-site continuous model describes adequately the experimental data. Moreover the values of apparent protonation constants (as adjustable parameters found by non-linear regression) are very near to the apparent constants evaluated by a Donnan model assuming the intrinsic constants in resin phase equal to the equilibrium constants in aqueous solution of ADA and considering the amphoteric nature of active sites for the evaluation of counter-ion concentration in the resin phase. Copper removal outlined the strong affinity of the active groups of the resin for this ion in solution compared to the S. natans biomass according to the complexation constants between aminodiacetic and mono-carboxylic groups and copper ions.

Investigation of the effect of hydroxypropyl methylcellulose on the phase transformation and release profiles of carbamazepine-nicotinamide cocrystal.

PubMed

Li, Mingzhong; Qiu, Shi; Lu, Yan; Wang, Ke; Lai, Xiaojun; Rehan, Mohammad

2014-09-01

The aim of this work was to investigate the influence of hydroxypropyl methylcellulose (HPMC) on the phase transformation and release profile of carbamazepine-nicotinamide (CBZ-NIC) cocrystal in solution and in sustained release matrix tablets. The polymorphic transitions of the CBZ-NIC cocrystal and its crystalline properties were examined by differential scanning calorimetry (DSC), X-ray powder diffraction (XRPD), Raman spectroscopy, and scanning electron microscopy (SEM). The apparent CBZ solubility and dissolution rate of CBZ-NIC cocrystal were constant in different concentrations of HPMC solutions. In a lower percentage of HPMC in the matrix tablets, the CBZ release profile of the CBZ-NIC cocrystal was nonlinear and declined over time. With an increased HPMC content in the tablets, the CBZ-NIC cocrystal formulation showed a significantly higher CBZ release rate in comparison with the other two formulations of CBZ III and the physical mixture. Because of a significantly improved dissolution rate of the CBZ-NIC cocrystal, the rate of CBZ entering into solution is significantly faster than the rate of formation of the CBZ-HPMC soluble complex in solution, leading to a higher supersaturation level of CBZ and subsequently precipitation of CBZ dihydrate.

Fluidization and drying of biomass particles in a vibrating fluidized bed with pulsed gas flow

DOE PAGES

Jia, Dening; Cathary, Océane; Peng, Jianghong; ...

2015-10-01

Fluidization of biomass particles in the absence of inert bed materials has been tested in a pulsed fluidized bed with vibration, with the pulsation frequency ranging from 033 to 6.67 Hz. Intermittent fluidization at 033 Hz and apparently 'normal' fluidization at 6.67 Hz with regular bubble patterns were observed. Pulsation has proven to be effective in overcoming the bridging of irregular biomass particles induced by strong inter-particle forces. The vibration is only effective when the pulsation is inadequate, either at too low a frequency or too low in amplitude. We dried biomass in order to quantify the effectiveness of gasmore » pulsation for fluidized bed dryers and torrefiers in terms of gas-solid contact efficiency and heat and mass transfer rates. Furthermore, the effects of gas flow rate, bed temperature, pulsation frequency and vibration intensity on drying performance have been systematically investigated. While higher temperature and gas flow rate are favored in drying, there exists an optimal range of pulsation frequency between 0.75 Hz and 1.5 Hz where gas-solid contact is enhanced in both the constant rate drying and falling rate drying periods.« less

Seafloor Uplift in Middle Valley, Juan de Fuca Ridge: New High-Resolution Pressure Data

NASA Astrophysics Data System (ADS)

Inderbitzen, K. E.; Becker, K.; Davis, E. E.

2011-12-01

Currently, in-situ seafloor and basement pressures are continuously monitored and recorded by an ODP subseafloor hydrogeological observatory (CORK) located in Middle Valley, Juan de Fuca Ridge. Hole 857D was drilled in 1991 in thickly sedimented crust to a depth of 936 mbsf and instrumented with an original CORK that was replaced in 1996. A large hydrothermal field (Dead Dog) lies roughly 1.7 km north of the hole, and two isolated chimneys and several diffuse flow sites are located ~800 meters northeast. The borehole and the vent fields have been visited periodically by submersible/ROV since 1999. Recent results from the CORK at 857D have shown apparent seafloor uplift, supported by depth records from the submersible Alvin. A constant rate of pressure change of ~6 kPa/yr, from its initiation in 2005 to the visit in 2010, has reduced mean seafloor pressure by ~28 kPa, equivalent to nearly 3 meters of head. This uplift rate is several times the typical pre-eruption inflation rates observed at Axial Seamount further south along the Juan de Fuca Ridge. Initially, the apparent uplift at 857D did not seem to have any effect on local high-temperature hydrothermal venting, however recent operations in Middle Valley revealed distinct changes at not only the hydrothermal field to the northeast, but also a shutdown of high-temperature venting to the north of 857D. We will present new data from Middle Valley, including the first year of data collected by a high-resolution pressure data logger deployed at 857D in June, 2010.

Crack Closure and Fatigue Crack Growth in 2219-T851 Aluminum Alloy

DTIC Science & Technology

1976-08-01

assumes the length of the crack perimeter to remain es - ’I sentially constant. At the maximum load, the crack is ap- proximately parabolic (or ellipical...for center cracked j specimens) in shape. With unloading, the parabola (or el- lipse) is collapsed. The resulting change in shape produces an apparent...reloading process, the electrical potential remained es - j sentially constant initially and was less than that at the corresponding load during unloading

Recommendations for terminology and databases for biochemical thermodynamics.

PubMed

Alberty, Robert A; Cornish-Bowden, Athel; Goldberg, Robert N; Hammes, Gordon G; Tipton, Keith; Westerhoff, Hans V

2011-05-01

Chemical equations are normally written in terms of specific ionic and elemental species and balance atoms of elements and electric charge. However, in a biochemical context it is usually better to write them with ionic reactants expressed as totals of species in equilibrium with each other. This implies that atoms of elements assumed to be at fixed concentrations, such as hydrogen at a specified pH, should not be balanced in a biochemical equation used for thermodynamic analysis. However, both kinds of equations are needed in biochemistry. The apparent equilibrium constant K' for a biochemical reaction is written in terms of such sums of species and can be used to calculate standard transformed Gibbs energies of reaction Δ(r)G'°. This property for a biochemical reaction can be calculated from the standard transformed Gibbs energies of formation Δ(f)G(i)'° of reactants, which can be calculated from the standard Gibbs energies of formation of species Δ(f)G(j)° and measured apparent equilibrium constants of enzyme-catalyzed reactions. Tables of Δ(r)G'° of reactions and Δ(f)G(i)'° of reactants as functions of pH and temperature are available on the web, as are functions for calculating these properties. Biochemical thermodynamics is also important in enzyme kinetics because apparent equilibrium constant K' can be calculated from experimentally determined kinetic parameters when initial velocities have been determined for both forward and reverse reactions. Specific recommendations are made for reporting experimental results in the literature. Copyright © 2011 Elsevier B.V. All rights reserved.

Modeling experimental stable isotope results from CO2 adsorption and diffusion experiments

NASA Astrophysics Data System (ADS)

Larson, T. E.

2012-12-01

Transport of carbon dioxide through porous media can be affected by diffusion, advection and adsorption processes. Developing new tools to understand which of these processes dominates migration of CO2 or other gases in the subsurface is important to a wide range of applications including CO2 storage. Whereas advection rates are not affected by isotope substitution in CO2, adsorption and diffusion constants are. For example, differences in the binary diffusion constant calculated between C12O2-He and C13O2-He results in a carbon isotope fractionation whereby the front of the chromatographic peak is enriched in carbon-12 and the tail of the peak is enriched in carbon-13. Interestingly, adsorption is shown to have an opposite, apparent inverse affect whereby the lighter isotopologues of CO2 are preferentially retained by the chromatographic column and the heavier isotopologues are eluted first. This apparent inverse chromatographic effect has been ascribed to Van der Waals dispersion forces. Smaller molar volumes of the heavier isotopologues resulting from increased bond strength (shorter bond length) effectively decreases Van der Waals forces in heavier isotopologues compared to lighter isotopologues. Here we discuss the possible application of stable isotope values measured across chromatographic peaks to differentiate diffusion-dominated from adsorption-dominated transport processes for CO2. Separate 1-dimensional flow-through columns were packed with quartz and illite, and one remained empty. Dry helium was used as a carrier gas. Constant flow rate, temperature and column pressure were maintained. After background CO2 concentrations were minimized and constant, a sustained pulse of CO2 was injected at the head of the column and the effluent was sampled at 4 minute intervals for CO2 concentration, and carbon and oxygen isotope ratios. The quartz-sand packed and empty columns resulted in similar trends in concentration and isotope ratios whereby CO2 concentrations steadily increased and became constant after two pore volumes of CO2 flushed through the column. Carbon and oxygen isotope values of the front of the peak (first pore volume) are 2‰ and 5‰ lower than the injected CO2 values, respectively. These results are fit very well using a mass transfer model that only includes binary diffusion between CO2 and helium that account for isotope substitution in the reduced mass coefficient. In contrast to these diffusion-dominated systems, CO2 break through curves from the illite packed column show strong adsorption effects that include a +180‰ increase in the carbon isotope ratio at the front of the peak followed by a 20‰ decrease. Up to 20 pore volumes of CO2 were flushed through the column before the carbon and oxygen isotope values stabilized to their starting values. These adsorption effects cannot be modeled using mass isotope effects alone, and instead must include additional parameters such as volume effects. These results demonstrate the importance of understanding the isotopic effects of CO2 in different substrates, and potentially offers a tracer tool that can be used to quantify surface area, transport distance, and surface reactivity of CO2. Additional applications may include more affectively determining transfer rates of CO2 across low permeability zones.

A tale of two cores: Evaluation of 210Pb dating methods of salt marsh sediments for two cores collected 30 years apart

NASA Astrophysics Data System (ADS)

Fuller, C.; Drexler, J. Z.

2016-12-01

210Pb dating of wetland sediments is commonly used to constrain recent C accumulation rates and contaminant input histories. However, uncertainties in 210Pb-derived rates and validation of accumulation and accretion rates using an independent tracer are often not reported. We describe here 210Pb and 137Cs profiles in two cores from a salt marsh in south San Francisco Bay, California, collected in 1981 and 2011 within 5 m of each other, to compare and evaluate 210Pb dating methods. In the 1981 core, unsupported 210Pb (210PbXS) was detected to 12 cm and yielded mass accumulation rates (MAR) of 0.043 and 0.036 g/cm2/y using the Constant Flux-Constant Sedimentation method (CF:CS) and Constant Rate of Supply (CRS) methods, respectively. Accretion rates (S) of 0.17 (CF:CS) and 0.12 cm/y (CRS) were calculated from these MARs. The distinct 137Cs peak at 4-6 cm in the 1981 core is in good agreement with the210Pb-based 1963 depth (3.4 and 4 cm, CF:CS and CRS, respectively). 210PbXS was detectable to 18 cm in the 2011 core, and yielded a CF:CS MAR (0.077 g/cm2/y; S = 0.35 cm/y) that is about two times greater than the mass-weighted average CRS MAR (0.044 g/cm2/y; S = 0.16 cm/y). Broad subsurface maxima in 137Cs and 239Pu were observed between 16 and 24 cm in the 2011 core, which are 5 to 11 cm deeper than the 1963 depth calculated by the 2011 and 1981 210Pb-derived MARs. The apparent migration and broadening of bomb-fallout radionuclide peaks over 30 years negates their use in validating 210Pb dating. Because of low 210PbXS activities in both cores, the base of the 210PbXS profile and integrated activity used in CRS are underestimated, resulting in the lower CRS MARs that decrease with increasing depth. The range of MARs determined for two cores within 5 m but separated by 30 years will be used as an example to evaluate the uncertainties that need to be reported with C accumulation rates and contaminant histories derived from 210Pb dating of sediment archives.

Sedimentation rates in Atibaia River basin, São Paulo State, Brazil, using 210Pb as geochronometer.

PubMed

Sabaris, T P P; Bonotto, D M

2011-01-01

The constant initial concentration (CIC) of unsupported/excess (210)Pb model was successfully used to assess (210)Pb data of nine sediment cores from Atibaia River basin, São Paulo State, Brazil. The (210)Pb-based apparent sediment mass accumulation rates ranged from 47.7 to 782.4 mg/cm(2)yr, whereas the average linear sedimentation rates between 0.16 and 1.32 cm/yr, which are compatible with the calculated sediment mass fluxes, i.e. a higher sediment mass accumulation rate yielded a higher linear sedimentation rate. The higher long-term based accumulation rate tended to be found in topographically softer regions. This occurs because the sediments are preferentially transported in topographically steeper regions instead of being deposited. Anthropic activities like deforestation possibly interfered with the natural/normal sedimentation processes, which increased in accordance with modifications on the channel drainage. The radionuclide geochronology as described in this paper allows determination of sedimentation rates that are compatible with values estimated elsewhere. The adoption of an appropriate factor generated from previous laboratory experiments resulted in a successful correction for the (222)Rn-loss from the sediments, bringing the estimate of the parent-supported (in-situ produced) (210)Pb to reliable values required by the CIC model. Copyright © 2010 Elsevier Ltd. All rights reserved.

Comminution of solids caused by kinetic energy of high shear strain rate, with implications for impact, shock, and shale fracturing.

PubMed

Bazant, Zdenek P; Caner, Ferhun C

2013-11-26

Although there exists a vast literature on the dynamic comminution or fragmentation of rocks, concrete, metals, and ceramics, none of the known models suffices for macroscopic dynamic finite element analysis. This paper outlines the basic idea of the macroscopic model. Unlike static fracture, in which the driving force is the release of strain energy, here the essential idea is that the driving force of comminution under high-rate compression is the release of the local kinetic energy of shear strain rate. The density of this energy at strain rates >1,000/s is found to exceed the maximum possible strain energy density by orders of magnitude, making the strain energy irrelevant. It is shown that particle size is proportional to the -2/3 power of the shear strain rate and the 2/3 power of the interface fracture energy or interface shear stress, and that the comminution process is macroscopically equivalent to an apparent shear viscosity that is proportional (at constant interface stress) to the -1/3 power of this rate. A dimensionless indicator of the comminution intensity is formulated. The theory was inspired by noting that the local kinetic energy of shear strain rate plays a role analogous to the local kinetic energy of eddies in turbulent flow.

The role of phosphates for the Lu-Hf chronology of meteorites

NASA Astrophysics Data System (ADS)

Debaille, Vinciane; Van Orman, James; Yin, Qing-Zhu; Amelin, Yuri

2017-09-01

The 176Lu-176Hf isotopic system is widely used for dating and tracing cosmochemical and geological processes, but still suffers from two uncertainties. First, Lu-Hf isochrons for some early Solar System materials have excess slope of unknown origin that should not be expected for meteorites with ages precisely determined with other isotopic chronometers. This observation translates to an apparent Lu decay constant higher than the one calculated by comparing ages obtained with various dating methods on terrestrial samples. Second, unlike the well constrained Sm/Nd value (to within 2%) for the chondritic uniform reservoir (CHUR), the Lu/Hf ratios in chondrites vary up to 18% when considering all chondrites, adding uncertainty to the Lu/Hf CHUR value. In order to better understand the Lu-Hf systematics of chondrites, we analyzed mineral fractions from the Richardton H5 chondrite to construct an internal Lu-Hf isochron, and set up a numerical model to investigate the effect of preferential diffusion of Lu compared to Hf from phosphate, the phase with the highest Lu-Hf ratio in chondrites, to other minerals. The isochron yields an age of 4647 ± 210 million years (Myr) using the accepted 176Lu decay constant of 1.867 ± 0.008 ×10-11yr-1. Combining this study with the phosphate fractions measured in a previous study yields a slope of 0.08855 ± 0.00072, translating to a 176Lu decay constant of 1.862 ± 0.016 ×10-11yr-1 using the Pb-Pb age previously obtained, in agreement with the accepted value. The large variation of the Lu/Hf phosphates combined with observations in the present study identify phosphates as the key in perturbing Lu-Hf dating and generating the isochron slope discrepancy. This is critical as apatite has substantially higher diffusion rates of rare earth elements than most silicate minerals that comprise stony meteorites. Results of numerical modeling depending of temperature peak, size of the grains and duration of the metamorphic event, show that diffusion processes in phosphate can produce an apparently older Lu-Hf isochron, while this effect will remain negligible in perturbing the Sm-Nd chronology. Our results suggest that only type 3 chondrites with the lowest metamorphic grade and large minerals with minimal diffusive effects are suitable for determination of the Lu-Hf CHUR values and the Lu decay constant respectively.

Modeling and validation of autoinducer-mediated bacterial gene expression in microfluidic environments

PubMed Central

Austin, Caitlin M.; Stoy, William; Su, Peter; Harber, Marie C.; Bardill, J. Patrick; Hammer, Brian K.; Forest, Craig R.

2014-01-01

Biosensors exploiting communication within genetically engineered bacteria are becoming increasingly important for monitoring environmental changes. Currently, there are a variety of mathematical models for understanding and predicting how genetically engineered bacteria respond to molecular stimuli in these environments, but as sensors have miniaturized towards microfluidics and are subjected to complex time-varying inputs, the shortcomings of these models have become apparent. The effects of microfluidic environments such as low oxygen concentration, increased biofilm encapsulation, diffusion limited molecular distribution, and higher population densities strongly affect rate constants for gene expression not accounted for in previous models. We report a mathematical model that accurately predicts the biological response of the autoinducer N-acyl homoserine lactone-mediated green fluorescent protein expression in reporter bacteria in microfluidic environments by accommodating these rate constants. This generalized mass action model considers a chain of biomolecular events from input autoinducer chemical to fluorescent protein expression through a series of six chemical species. We have validated this model against experimental data from our own apparatus as well as prior published experimental results. Results indicate accurate prediction of dynamics (e.g., 14% peak time error from a pulse input) and with reduced mean-squared error with pulse or step inputs for a range of concentrations (10 μM–30 μM). This model can help advance the design of genetically engineered bacteria sensors and molecular communication devices. PMID:25379076

Oxidation of cetirizine, fexofenadine and hydrochlorothiazide during ozonation: Kinetics and formation of transformation products.

PubMed

Borowska, Ewa; Bourgin, Marc; Hollender, Juliane; Kienle, Cornelia; McArdell, Christa S; von Gunten, Urs

2016-05-01

The efficiency of wastewater ozonation for the abatement of three nitrogen-containing pharmaceuticals, two antihistamine drugs, cetirizine (CTR) and fexofenadine (FXF), and the diuretic drug, hydrochlorothiazide (HCTZ), was investigated. Species-specific second-order rate constants for the reactions of the molecular, protonated (CTR, FXF) or deprotonated (HCTZ) forms of these compounds with ozone were determined. All three compounds are very reactive with ozone (apparent second order rate constants at pH 7: kO3,pH7 = 1.7·10(5) M(-1)s(-1), 8.5·10(4) M(-1)s(-1) and 9.0·10(3) M(-1)s(-1) for CTR, HCTZ and FXF, respectively). Transformation product (TP) structures were elucidated using liquid chromatography coupled with high-resolution tandem mass spectrometry, including isotope-labeled standards. For cetirizine and hydrochlorothiazide 8 TPs each and for fexofenadine 7 TPs were identified. The main TPs of cetirizine and fexofenadine are their respective N-oxides, whereas chlorothiazide forms to almost 100% from hydrochlorothiazide. In the bacteria bioluminescence assay the toxicity was slightly increased only during the ozonation of cetirizine at very high cetirizine concentrations. The main TPs detected in bench-scale experiments were also detected in full-scale ozonation of a municipal wastewater, for >90% elimination of the parent compounds. Copyright © 2016 Elsevier Ltd. All rights reserved.

The characterization of the adsorption of cadmium from aqueous solution using natural fibers treated with nanoparticles

NASA Astrophysics Data System (ADS)

Rediske, Nicole M.

The objective of this research was to characterize natural carbon fibers from coconut husks, both bare and impregnated with metallic nanoparticles, in removing cadmium from aqueous media. The adsorbent load, kinetics, isotherm parameters, removal efficiencies, desorption capacity and possible contaminant removal mechanisms were evaluated. It was found that the fibers treated with metallic nanoparticles performed better than the bare fibers in removing cadmium from water. The ideal conditions were found to be neutral pH with low initial cadmium concentrations. Through the kinetic analyses, the adsorption process was first thought to be pseudo first order with two separate adsorption mechanisms apparent. Upon further analysis, it was seen that the first mechanism does not follow the pseudo first order kinetics model. An increase in calcium and magnesium concentrations was observed as the cadmium concentrations decreases. This increase corresponds with first mechanism. This suggests the cadmium removal in the first mechanism is due to ion exchange. The second mechanism's rate constant was consistently lower than the first mechanisms rate constant by an order of magnitude. This led to the hypothesis that the second mechanism is controlled by van de Waals forces, specifically ion-induced dipole interactions, and physical adsorption. It was also found that the cadmium does not effectively desorb from the wasted fibers in DI water. Keywords: Adsorption; kinetics; pseudo first order; cadmium; metallic nanoparticles; natural fibers; removal efficiencies; ion exchange.

Influence of different nominal molecular weight fractions of humic acids on phenol oxidation by permanganate.

PubMed

He, Di; Guan, Xiaohong; Ma, Jun; Yu, Min

2009-11-01

The effects of humic acid (HA) and its different nominal molecular weight (NMW) fractions on the phenol oxidation by permanganate were studied. Phenol oxidation by permanganate was enhanced by the presence of HA at pH 4-8, while slightly inhibited at pH 9-10. The effects of HA on phenol oxidation by permanganate were dependent on HA concentration and permanganate/phenol molar ratios. The high NMW fractions of HA enhanced phenol oxidation by permanganate at pH 7 more significantly than the low fractions of HA. The apparent second-order rate constants of phenol oxidation by permanganate in the presence of HA correlated well with their specific ultraviolet absorption (SUVA) at 254 nm and specific violet absorption (SVA) at 465 or 665 nm. High positive correlation coefficients (R(2) > 0.72) implied that pi-electrons of HA strongly influenced the reactivity of phenol towards permanganate oxidation which agreed well with the information provided by fluorescence spectroscopy. The FTIR analysis indicated that the HA fractions rich in aliphatic character, polysaccharide-like substances, and the amount of carboxylate groups had less effect on phenol oxidation by permanganate. The negative correlation between the rate constants of phenol oxidation by permanganate and O/C ratios suggested that the oxidation of phenol increased with a decrease in the content of oxygen-containing functional groups.

Cyclopropyl conjugation and ketyl anions: when do things begin to fall apart?

PubMed

Tanko, J M; Li, Xiangzhong; Chahma, M'hamed; Jackson, Woodward F; Spencer, Jared N

2007-04-11

Results pertaining to the electrochemical reduction of 1,2-diacetylcyclopropane (5), 1-acetyl-2-phenylcyclopropane (6), 1-acetyl-2-benzoylcyclopropane (7), and 1,2-dibenzoylcyclopropane (8) are reported. While 6*- exists as a discrete species, the barrier to ring opening is very small (<1 kcal/mol) and the rate constant for ring opening is >10(7) s(-1). For 7 and 8, the additional resonance stabilization afforded by the benzoyl moieties results in significantly lower rate constants for ring opening, on the order of 10(5)-10(6) s(-1). Electron transfer to 8 serves to initiate an unexpected vinylcyclopropane --> cyclopentene type rearrangement, which occurs via a radical ion chain mechanism. The results for reduction of 5 are less clear-cut: The experimental results suggest that the reduction is unexceptional, with a symmetry coefficient alpha

High yield of secondary B-side electron transfer in mutant Rhodobacter capsulatus reaction centers

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

Kressel, Lucas; Faries, Kaitlyn M.; Wander, Marc J.

2014-08-01

From the crystal structures of reaction centers (RCs) from purple photosynthetic bacteria, two pathways for electron transfer (ET) are apparent but only one pathway (the A side) operates in the native protein-cofactor complex. Partial activation of the B-side pathway has unveiled the true inefficiencies of ET processes on that side in comparison to analogous reactions on the A side. Of significance are the relative rate constants for forward ET and the competing charge recombination reactions. On the B side, these rate constants are nearly equal for the secondary charge-separation step (ET from bacteriopheophytin to quinone), relegating the yield of thismore » process to < 50%. Herein we report efforts to optimize this step. In surveying all possible residues at position 131 in the M subunit, we discovered that when glutamic acid replaces the native valine the efficiency of the secondary ET is nearly two-fold higher than in the wild-type RC. The positive effect of M131 Glu is likely due to formation of a hydrogen bond with the ring V keto group of the B-side bacteriopheophytin leading to stabilization of the charge-separated state involving this cofactor. In conclusion, this change slows charge recombination by roughly a factor of two and affords the improved yield of the desired forward ET to the B-side quinone terminal acceptor.« less

Opicapone: a short lived and very long acting novel catechol-O-methyltransferase inhibitor following multiple dose administration in healthy subjects

PubMed Central

Rocha, José Francisco; Almeida, Luis; Falcão, Amílcar; Palma, P Nuno; Loureiro, Ana I; Pinto, Roberto; Bonifácio, Maria João; Wright, Lyndon C; Nunes, Teresa; Soares-da-Silva, Patrício

2013-01-01

Aims The aim of this study was to assess the tolerability, pharmacokinetics and inhibitory effect on erythrocyte soluble catechol-O-methyltransferase (S-COMT) activity following repeated doses of opicapone. Methods This randomized, placebo-controlled, double-blind study enrolled healthy male subjects who received either once daily placebo or opicapone 5, 10, 20 or 30 mg for 8 days. Results Opicapone was well tolerated. Its systemic exposure increased in an approximately dose-proportional manner with an apparent terminal half-life of 1.0 to 1.4 h. Sulphation was the main metabolic pathway. Opicapone metabolites recovered in urine accounted for less than 3% of the amount of opicapone administered suggesting that bile is likely the main route of excretion. Maximum S-COMT inhibition (Emax) ranged from 69.9% to 98.0% following the last dose of opicapone. The opicapone-induced S-COMT inhibition showed a half-life in excess of 100 h, which was dose-independent and much longer than plasma drug exposure. Such a half-life translates into a putative underlying rate constant that is comparable with the estimated dissociation rate constant of the COMT–opicapone complex. Conclusion Despite its short elimination half-life, opicapone markedly and sustainably inhibited erythrocyte S-COMT activity making it suitable for a once daily regimen. PMID:23336248

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br

NASA Technical Reports Server (NTRS)

Hsu, K.-J.; Demore, W. B.

1994-01-01

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2) and (for CH2Cl2) HFC-161 (CH3CH2F). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.

Anti-Arrhenius cleavage of covalent bonds in bottlebrush macromolecules on substrate.

PubMed

Lebedeva, Natalia V; Nese, Alper; Sun, Frank C; Matyjaszewski, Krzysztof; Sheiko, Sergei S

2012-06-12

Spontaneous degradation of bottlebrush macromolecules on aqueous substrates was monitored by atomic force microscopy. Scission of C ─ C covalent bonds in the brush backbone occurred due to steric repulsion between the adsorbed side chains, which generated bond tension on the order of several nano-Newtons. Unlike conventional chemical reactions, the rate of bond scission was shown to decrease with temperature. This apparent anti-Arrhenius behavior was caused by a decrease in the surface energy of the underlying substrate upon heating, which results in a corresponding decrease of bond tension in the adsorbed macromolecules. Even though the tension dropped minimally from 2.16 to 1.89 nN, this was sufficient to overpower the increase in the thermal energy (k(B)T) in the Arrhenius equation. The rate constant of the bond-scission reaction was measured as a function of temperature and surface energy. Fitting the experimental data by a perturbed Morse potential V = V(0)(1 - e(-βx))(2) - fx, we determined the depth and width of the potential to be V(0) = 141 ± 19 kJ/mol and β(-1) = 0.18 ± 0.03 Å, respectively. Whereas the V(0) value is in reasonable agreement with the activation energy E(a) = 80-220 kJ/mol of mechanical and thermal degradation of organic polymers, it is significantly lower than the dissociation energy of a C ─ C bond D(e) = 350 kJ/mol. Moreover, the force constant K(x) = 2β(2)V(0) = 1.45 ± 0.36 kN/m of a strained bottlebrush along its backbone is markedly larger than the force constant of a C ─ C bond K(l) = 0.44 kN/m, which is attributed to additional stiffness due to deformation of the side chains.

Study on COD removal mechanism and reaction kinetics of oilfield wastewater.

PubMed

Yin, Xian-Qing; Jing, Bo; Chen, Wen-Juan; Zhang, Jian; Liu, Qian; Chen, Wu

2017-11-01

The chemical oxygen demand (COD) removal mechanism and reaction kinetics were mainly studied in the treatment of oilfield oily sewage containing polymer by three-dimensional electrode reactor. The results proved that the residual active oxides O 3 , H 2 O 2 , •OH and active chlorine in the system of electrochemical reaction could be effectively detected, and the COD removal mechanism was co-oxidation of active oxides; Under these experimental conditions: the electrolysis current of 6 A, surface/volume ratio of 6/25(cm 2 ·L -1 ), the reaction time of 50 min, the COD cr of treated sewage was no more than 50 mg·L -1 ; the removal reaction of COD conformed to apparent second-order reaction kinetic model, the correlation coefficient R 2 was 0.9728, and the apparent reaction rate constant was k = 3.58 × 10 -4 (L·min -1 ·mg -1 ·m -2 ). To reach the goal, the COD cr was no more than 50 mg·L -1 in treated sewage, and the theory minimum processing time was 45.73 min. The verification of experimental results was consistent with kinetic equations.

Dissolution kinetics of volatile organic compound vapors in water: An integrated experimental and computational study

NASA Astrophysics Data System (ADS)

Mahmoodlu, Mojtaba G.; Pontedeiro, Elizabeth M.; Pérez Guerrero, Jesús S.; Raoof, Amir; Majid Hassanizadeh, S.; van Genuchten, Martinus Th.

2017-01-01

In this study we performed batch experiments to investigate the dissolution kinetics of trichloroethylene (TCE) and toluene vapors in water at room temperature and atmospheric pressure. The batch systems consisted of a water reservoir and a connected headspace, the latter containing a small glass cylinder filled with pure volatile organic compound (VOC). Results showed that air phase concentrations of both TCE and toluene increased relatively quickly to their maximum values and then became constant. We considered subsequent dissolution into both stirred and unstirred water reservoirs. Results of the stirred experiments showed a quick increase in the VOC concentrations with time up to their solubility limit in water. VOC vapor dissolution was found to be independent of pH. In contrast, salinity had a significant effect on the solubility of TCE and toluene vapors. VOC evaporation and vapor dissolution in the stirred water reservoirs followed first-order rate processes. Observed data could be described well using both simplified analytical solutions, which decoupled the VOC dynamics in the air and water phases, as well as using more complete coupled solutions. However, the estimated evaporation (ke) and dissolution (kd) rate constants differed by up to 70% between the coupled and uncoupled formulations. We also numerically investigated the effects of fluid withdrawal from the small water reservoir due to sampling. While decoupling the VOC air and water phase mass transfer processes produced unreliable estimates of kd, the effects of fluid withdrawal on the estimated rate constants were found to be less important. The unstirred experiments showed a much slower increase in the dissolved VOC concentrations versus time. Molecular diffusion of the VOCs within the aqueous phase became then the limiting factor for mass transfer from air to water. Fluid withdrawal during sampling likely caused some minor convection within the reservoir, which was simulated by increasing the apparent liquid diffusion coefficient.

Kinetics of oxygen consumption after a single flash of light in photoreceptors of the drone (Apis mellifera)

PubMed Central

1982-01-01

The time course of the rate of oxygen consumption (QO2) after a single flash of light has been measured in 300-micrometers slices of drone retina at 22 degrees C. To measure delta QO2(t), the change in QO2 from its level in darkness, the transients of the partial pressure of O2 (PO2) were recorded with O2 microelectrodes simultaneously in two sites in the slice and delta QO2 was calculated by a computer using Fourier transforms. After a 40-ms flash of intense light, delta QO2, reached a peak of 40 microliters O2/g.min and then declined exponentially to the baseline with a time constant tau 1 = 4.96 +/- 0.49 s (SD, n = 10). The rising phase was characterized by a time constant tau 2 = 1.90 +/- 0.35 s (SD, n = 10). The peak amplitude of delta QO2 increased linearly with the log of the light intensity. Replacement of Na+ by choline, known to decrease greatly the light-induced transmembrane current, caused a 63% decrease of delta QO2. With these changes, however, the kinetics of delta QO2 (t) were unchanged. This suggest that the recovery phase is rate-limited by a single reaction with apparent first-order kinetics. Evidence is provided that suggests that this reaction may be the working of the sodium pump. Exposure of the retina to high concentrations of ouabain or strophanthidin (inhibitors of the sodium pump) reduced the peak amplitude of delta QO2 by approximately 80% and increased tau 1. The increase of tau 1 was an exponential function of the time of exposure to the cardioactive steroids. Hence, it seems likely that the greatest part of delta QO2 is used for the working of the pump, whose activity is the mechanism underlying the rate constant of the descending limb of delta QO2 (t). PMID:6288837

[Kinetics modeling and reaction mechanism of ferrate(VI) oxidation of triclosan].

PubMed

Yang, Bin; Ying, Guang-Guo; Zhao, Jian-Liang

2011-09-01

Triclosan (TCS) is a broad-spectrum antibacterial agent widely used in many personal care products. We investigated oxidation of TCS by aqueous ferrate Fe(VI) to determine reaction kinetics, interpreted the reaction mechanism by a linear free-energy relationship, and evaluated the degradation efficiency. Second-order reaction kinetics was used to model Fe (VI) oxidation of TCS, with the apparent second-order rate constant (k(app)) being 531.9 L x (mol x s)(-1) at pH 8.5 and (24 +/- 1) degrees C. The half life (t1/2) is 25.8 s for an Fe( VI) concentration of 10 mg x L(-1). The rate constants of the reaction decrease with increasing pH values. These pH-dependent variations in k(app) could be distributed by considering species-specific reactions between Fe(VI) species and acid-base species of an ionizable TCS. Species-specific second-order reaction rate constants, k, were determined for reaction of HFeO4(-) with each of TCS's acid-base species. The value of k determined for neutral TCS was (4.1 +/- 3.5) x 10(2) L x (mol x s)(-1), while that measured for anionic TCS was (1.8 +/- 0.1) x 10(4) L x (mol x s)(-1). The reaction between HFeO4(-) and the dissociated TCS controls the overall reaction. A linear free-energy relationship illustrated the electrophilic oxidation mechanism. Fe (VI) reacts initially with TCS by electrophilic attack at the latter's phenol moiety. At a n[Fe(VI)]: n(TCS) > 7: 1, complete removal of TCS was achieved. And lower concentration of the humic acid could enhance the k(app) of Fe( VI) with TCS. In conclusion, Fe(VI) oxidation technology appears to be a promising tool for applications of WWTPs effluents and other decontamination processes.

Assessment of microbial methane oxidation above a petroleum-contaminated aquifer using a combination of in situ techniques

NASA Astrophysics Data System (ADS)

Urmann, Karina; Schroth, Martin H.; Noll, Matthias; Gonzalez-Gil, Graciela; Zeyer, Josef

2008-06-01

Emissions of the greenhouse gas CH4, which is often produced in contaminated aquifers, are reduced or eliminated by microbial CH4 oxidation in the overlying vadose zone. The aim of this field study was to estimate kinetic parameters and isotope fractionation factors for CH4 oxidation in situ in the vadose zone above a methanogenic aquifer in Studen, Switzerland, and to characterize the involved methanotrophic communities. To quantify kinetic parameters, several field tests, so-called gas push-pull tests (GPPTs), with CH4 injection concentrations ranging from 17 to 80 mL L-1 were performed. An apparent Vmax of 0.70 ± 0.15 mmol CH4 (L soil air)-1 h-1 and an apparent Km of 0.28 ± 0.09 mmol CH4 (L soil air)-1 was estimated for CH4 oxidation at 2.7 m depth, close to the groundwater table. At 1.1 m depth, Km (0.13 ± 0.02 mmol CH4 (L soil air)-1) was in a similar range, but Vmax (0.076 ± 0.006 mmol CH4 (L soil air)-1 h-1) was an order of magnitude lower. At 2.7 m, apparent first-order rate constants determined from a CH4 gas profile (1.9 h-1) and from a single GPPT (2.0 ± 0.03 h-1) were in good agreement. Above the groundwater table, a Vmax much higher than the in situ CH4 oxidation rate prior to GPPTs indicated a high buffer capacity for CH4. At both depths, known methanotrophic species affiliated with Methylosarcina and Methylocystis were detected by cloning and sequencing. Apparent stable carbon isotope fractionation factors α for CH4 oxidation determined during GPPTs ranged from 1.006 to 1.032. Variability was likely due to differences in methanotrophic activity and CH4 availability leading to different degrees of mass transfer limitation. This complicates the use of stable isotopes as an independent quantification method.

Control of the Protein Turnover Rates in Lemna minor

PubMed Central

Trewavas, A.

1972-01-01

The control of protein turnover in Lemna minor has been examined using a method described in the previous paper for determining the rate constants of synthesis and degradation of protein. If Lemna is placed on water, there is a reduction in the rate constants of synthesis of protein and an increase (3- to 6-fold) in the rate constant of degradation. The net effect is a loss of protein from the tissue. Omission of nitrate, phosphate, sulfate, magnesium, or calcium results in increases in the rate constant of degradation of protein. An unusual dual effect of benzyladenine on the turnover constants has been observed. Treatment of Lemna grown on sucrose-mineral salts with benzyladenine results in alterations only in the rate constant of synthesis. Treatment of Lemna grown on water with benzyladenine alters only the rate constant of degradation. Abscisic acid on the other hand alters both rate constants of synthesis and degradation of protein together. Inclusion of growth-inhibiting amino acids in the medium results in a reduction in the rate constants of synthesis and increases in the rate constant of degradation of protein. It is concluded that the rate of turnover of protein in Lemna is very dependent on the composition of the growth medium. Conditions which reduce growth rates also reduce the rates of synthesis of protein and increase those of degradation. PMID:16657895

Novel bio-electro-Fenton technology for azo dye wastewater treatment using microbial reverse-electrodialysis electrolysis cell.

PubMed

Li, Xiaohu; Jin, Xiangdan; Zhao, Nannan; Angelidaki, Irini; Zhang, Yifeng

2017-03-01

Development of sustainable technologies for treatment of azo dyes containing wastewaters has long been of great interest. In this study, we proposed an innovative concept of using microbial reverse-electrodialysis electrolysis cell (MREC) based Fenton process to treat azo dye wastewater. In such MREC-Fenton integrated process, the production of H 2 O 2 which is the key reactant of fenton-reaction was driven by the electrons harvested from the exoelectrogens and salinity-gradient between sea water and fresh water in MREC. Complete decolorization and mineralization of 400mgL -1 Orange G was achieved with apparent first order rate constants of 1.15±0.06 and 0.26±0.03h -1 , respectively. Furthermore, the initial concentration of orange G, initial solution pH, catholyte concentration, high and low concentration salt water flow rate and air flow rate were all found to significantly affect the dye degradation. This study provides an efficient and cost-effective system for the degradation of non-biodegradable pollutants. Copyright © 2017 Elsevier Ltd. All rights reserved.

Advantageous Solubility-Permeability Interplay When Using Amorphous Solid Dispersion (ASD) Formulation for the BCS Class IV P-gp Substrate Rifaximin: Simultaneous Increase of Both the Solubility and the Permeability.

PubMed

Beig, Avital; Fine-Shamir, Noa; Lindley, David; Miller, Jonathan M; Dahan, Arik

2017-05-01

Rifaximin is a BCS class IV (low-solubility, low-permeability) drug and also a P-gp substrate. The aims of this work were to assess the efficiency of different rifaximin amorphous solid dispersion (ASDs) formulations in achieving and maintaining supersaturation and to investigate the consequent solubility-permeability interplay. Spray-dried rifaximin ASDs were prepared with different hydrophilic polymers and their ability to achieve and maintain supersaturation was assessed. Then, rifaximin's apparent intestinal permeability was investigated as a function of increasing supersaturation both in vitro using the parallel artificial membrane permeability assay (PAMPA) and in vivo using the single-pass rat intestinal perfusion (SPIP) model. The efficiency of the different ASDs to achieve and maintain supersaturation of rifaximin was found to be highly polymer dependent, and the copovidone/HPC-SL formulation was found to be superior to the other two, allowing supersaturation of 200× that of the crystalline solubility for 20 h. In vitro, rifaximin flux was increased and the apparent permeability was constant as a function of increasing supersaturation level. In vivo, on the other hand, absorption rate coefficient (k a ) was first constant as a function of increasing supersaturation, but at 250×, the crystalline solubility k a was doubled, similar to the k a in the presence of the strong P-gp inhibitor GF120918. In conclusion, a new and favorable nature of solubility-permeability interplay was revealed in this work: delivering high supersaturation level of the BCS class IV drug rifaximin via ASD, thereby saturating the drugs' P-gp-mediated efflux transport, led to the favorable unique win-win situation, where both the solubility and the permeability increased simultaneously.

A pK change of acidic residues contributes to cation countertransport in the Ca-ATPase of sarcoplasmic reticulum. Role of H+ in Ca(2+)-ATPase countertransport.

PubMed

Yu, X; Hao, L; Inesi, G

1994-06-17

Proteoliposomal vesicles reconstituted with sarcoplasmic reticulum ATPase and exogenous lipids sustain ATP-dependent Ca2+ uptake and H+ ejection, as well as net charge displacement by Ca2+. We have studied the effect of lumenal (inner) and medium (extravesicular) pH variations on the countertransport ratios of H+ and Ca2+. We find that the Ca2+/H+ molar ratio is approximately 1 when the lumenal and medium pH is near neutrality, but changes with a specific pattern when the medium pH is varied in the presence of a constant lumenal pH and when the lumenal pH is varied in the presence of a constant medium pH. Empirical analysis of the experimental data shows that the apparent pK of the residue(s) releasing H+ into the medium is approximately 6.1, whereas the apparent pK of the residue(s) binding lumenal H+ is approximately 7.7. Assuming that the same acidic residues are involved in H+ and Ca2+ countertransport, our findings suggest a lower affinity for H+ in their outward orientation (prevalent in the ground state of the enzyme) and a higher affinity for H+ in lumenal orientation (prevalent in the phosphorylated state of the enzyme). Cyclic pK changes, coupled to ATP utilization, promote cation exchange, Ca2+ uptake, and H+ ejection by the vesicles. The stoichiometry of countertransport and net charge displacement is matched by a corresponding electrogenic behavior. A calculation of voltage development related to initial rates of charge transfer (dV/dt = (dQ/dt)/Cm) is given as a corrective replacement of a previous steady state calculation.

Single-Dose Pharmacokinetics of a Pleconaril (VP63843) Oral Solution in Children and Adolescents

PubMed Central

Kearns, Gregory L.; Abdel-Rahman, Susan M.; James, Laura P.; Blowey, Douglas L.; Marshall, James D.; Wells, Thomas G.; Jacobs, Richard F.

1999-01-01

Pleconaril is an orally active, broad-spectrum antipicornaviral agent which demonstrates excellent penetration into the central nervous system, liver, and nasal epithelium. In view of the potential pediatric use of pleconaril, we conducted a single-dose, open-label study to characterize the pharmacokinetics of this antiviral agent in pediatric patients. Following an 8- to 10-h period of fasting, 18 children ranging in age from 2 to 12 years (7.5 ± 3.1 years) received a single 5-mg/kg of body weight oral dose of pleconaril solution administered with a breakfast of age-appropriate composition. Repeated blood samples (n = 10) were obtained over 24 h postdose, and pleconaril was quantified from plasma by gas chromatography. Plasma drug concentration-time data for each subject were fitted to the curve by using a nonlinear, weighted (weight = 1/Ycalc) least-squares algorithm, and model-dependent pharmacokinetic parameters were determined from the polyexponential parameter estimates. Pleconaril was well tolerated by all subjects. A one-compartment open-model with first-order absorption best described the plasma pleconaril concentration-time profile in 13 of the subjects over a 24-h postdose period. Pleconaril pharmacokinetic parameters (means ± standard deviations) for these 13 patients were as follows. The maximum concentration of the drug in serum (Cmax) was 1,272.5 ± 622.1 ng/ml. The time to Cmax was 4.1 ± 1.5 h, and the lag time was 0.75 ± 0.56 h. The apparent absorption rate constant was 0.75 ± 0.48 1/h, and the elimination rate constant was 0.16 ± 0.07 1/h. The area under the concentration-time curve from 0 to 24 h was 8,131.15 ± 3,411.82 ng · h/ml. The apparent total plasma clearance was 0.81 ± 0.86 liters/h/kg, and the apparent steady-state volume of distribution was 4.68 ± 2.02 liters/kg. The mean elimination half-life of pleconaril was 5.7 h. The mean plasma pleconaril concentrations at both 12 h (250.4 ± 148.2 ng/ml) and 24 h (137.9 ± 92.2 ng/ml) after the single 5-mg/kg oral dose in children were higher than that from in vitro studies reported to inhibit >90% of nonpolio enterovirus serotypes (i.e., 70 ng/ml). Thus, our data support the evaluation of a 5-mg/kg twice-daily oral dose of pleconaril for therapeutic trials in pediatric patients with enteroviral infections. PMID:10049279

HENRY'S LAW CONSTANTS AND MICELLAR PARTITIONING OF VOLATILE ORGANIC COMPOUNDS IN SURFACTANT SOLUTIONS

EPA Science Inventory

Partitioning of volatile organic compounds (VOCs) into surfactant micelles affects the apparent vapor-liquid equilibrium of VOCs in surfactant solutions. This partitioning will complicate removal of VOCs from surfactant solutions by standard separation processes. Headspace expe...

Voltage gating by molecular subunits of Na+ and K+ ion channels: higher-dimensional cubic kinetics, rate constants, and temperature.

PubMed

Fohlmeister, Jürgen F

2015-06-01

The structural similarity between the primary molecules of voltage-gated Na and K channels (alpha subunits) and activation gating in the Hodgkin-Huxley model is brought into full agreement by increasing the model's sodium kinetics to fourth order (m(3) → m(4)). Both structures then virtually imply activation gating by four independent subprocesses acting in parallel. The kinetics coalesce in four-dimensional (4D) cubic diagrams (16 states, 32 reversible transitions) that show the structure to be highly failure resistant against significant partial loss of gating function. Rate constants, as fitted in phase plot data of retinal ganglion cell excitation, reflect the molecular nature of the gating transitions. Additional dimensions (6D cubic diagrams) accommodate kinetically coupled sodium inactivation and gating processes associated with beta subunits. The gating transitions of coupled sodium inactivation appear to be thermodynamically irreversible; response to dielectric surface charges (capacitive displacement) provides a potential energy source for those transitions and yields highly energy-efficient excitation. A comparison of temperature responses of the squid giant axon (apparently Arrhenius) and mammalian channel gating yields kinetic Q10 = 2.2 for alpha unit gating, whose transitions are rate-limiting at mammalian temperatures; beta unit kinetic Q10 = 14 reproduces the observed non-Arrhenius deviation of mammalian gating at low temperatures; the Q10 of sodium inactivation gating matches the rate-limiting component of activation gating at all temperatures. The model kinetics reproduce the physiologically large frequency range for repetitive firing in ganglion cells and the physiologically observed strong temperature dependence of recovery from inactivation. Copyright © 2015 the American Physiological Society.

Gold nanoworms immobilized graphene oxide polymer brush nanohybrid for catalytic degradation studies of organic dyes

NASA Astrophysics Data System (ADS)

Mogha, Navin Kumar; Gosain, Saransh; Masram, Dhanraj T.

2017-02-01

In the present work, we report gold nanoparticles (AuNPs) on poly (dimethylaminoethyl methacrylate) (PDMAEMA) brushes immobilized reduced graphene oxide (Au/PDMAEMA/RGO) as catalyst for degradation kinetic studies of Rhodamine B (RB), Methyl Orange (MO) and Eosine Y (EY) dyes, having an excellent catalytic activity, as evident by the apparent rate constant (kapp), which is found to be 21.8, 26.2, and 8.7 (×10-3 s-1), for RB, MO and EY respectively. Au/PDMAEMA/RGO catalyst is easy to use, highly efficient, recyclable, which make it suitable for applications in waste water management. Foremost, synthesis of PDMAEMA brushes on graphene oxide is accomplished by Atom transfer radical polymerization method (ATRP), whereas AuNPs are synthesized by simple chemical reduction method.

Self-Powered Adaptive Switched Architecture Storage

NASA Astrophysics Data System (ADS)

El Mahboubi, F.; Bafleur, M.; Boitier, V.; Alvarez, A.; Colomer, J.; Miribel, P.; Dilhac, J.-M.

2016-11-01

Ambient energy harvesting coupled to storage is a way to improve the autonomy of wireless sensors networks. Moreover, in some applications with harsh environment or when a long service lifetime is required, the use of batteries is prohibited. Ultra-capacitors provide in this case a good alternative for energy storage. Such storage must comply with the following requirements: a sufficient voltage during the initial charge must be rapidly reached, a significant amount of energy should be stored and the unemployed residual energy must be minimised at discharge. To answer these apparently contradictory criteria, we propose a selfadaptive switched architecture consisting of a matrix of switched ultra-capacitors. We present the results of a self-powered adaptive prototype that shows the improvement in terms of charge time constant, energy utilization rate and then energy autonomy.

Modelling of polymer photodegradation for solar cell modules

NASA Technical Reports Server (NTRS)

Somersall, A. C.; Guillet, J. E.

1981-01-01

A computer model including an integration routine was developed and demonstrated to simulate, in principle, the chemical changes which may occur in the photooxidation of hydrocarbons, using as input data a set of elementary reactions, corresponding rate constants and appropriate starting conditions. Application of this model to the photooxidation of pottant and plastic materials used in the LSA module designs provides a reliable predictive capability regarding the useful lifetime of these materials. An earlier mechanism consisting of 46 reactions was simplified considerably by reducing the number of formal termination steps since it became apparent that the major termination process goes via the peroxy radicals. In addition, new reactions of oxygen with acryl radicals (from Norrish type I) to form peracids, which then decompose to form carbon dioxide are included.

Nonintrinsic origin of the colossal dielectric constants in Ca Cu3 Ti4 O12

NASA Astrophysics Data System (ADS)

Lunkenheimer, P.; Fichtl, R.; Ebbinghaus, S. G.; Loidl, A.

2004-11-01

The dielectric properties of CaCu3Ti4O12 , a material showing colossal values of the dielectric constant, were investigated over a broad temperature and frequency range extending up to 1.3GHz . A detailed equivalent-circuit analysis of the results and two crucial experiments, employing different types of contacts and varying the sample thickness were performed. The results provide clear evidence that the apparently high values of the dielectric constant in CaCu3Ti4O12 are nonintrinsic and due to electrode polarization effects. The intrinsic properties of CaCu3Ti4O12 are characterized by charge transport via hopping of localized charge carriers and a relatively high dielectric constant of the order of 100.

Observation of Failure and Domain Switching in Lead Zirconate Titanate Ceramics

NASA Astrophysics Data System (ADS)

Okayasu, Mitsuhiro; Sugiyama, Eriko; Sato, Kazuto; Mizuno, Mamoru

The mechanical and electrical properties (electromechanical coupling coefficient, piezoelectric constant and dielectric constant) of lead zirconate titanate (PZT) ceramics are investigated during mechanical static and cyclic loading. There are several failure characteristics which can alter the material properties of PZT ceramics. The elastic constant increases and electrical properties decrease with increasing the applied load. This is due to the internal strain arising from the domain switching. In this case, 90° domain switching occurs anywhere in the samples as the sample is loaded. It is also apparent that electrogenesis occurs several times during cyclic loading to the final fracture. This occurrence is related to the domain switching. The elastic constant and electrical properties can decrease because of crack generation in the PZT ceramics. Moreover, the elastic constant increases with increase of the mechanical load and decreases with decrease of the load. On the contrary, the opposite sense of change of the electrical properties is observed.

Indication, from Pioneer 10/11, Galileo, and Ulysses Data, of an Apparent Anomalous, Weak, Long-Range Acceleration

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

Anderson, J.D.; Lau, E.L.; Turyshev, S.G.

Radio metric data from the Pioneer 10/11, Galileo, and Ulysses spacecraft indicate an apparent anomalous, constant, acceleration acting on the spacecraft with a magnitude {approximately}8.5{times}10{sup {minus}8} cm/s{sup 2} , directed towards the Sun. Two independent codes and physical strategies have been used to analyze the data. A number of potential causes have been ruled out. We discuss future kinematic tests and possible origins of the signal. {copyright} {ital 1998} {ital The American Physical Society}

Thermosensitive polymer stabilized core-shell AuNR@Ag nanostructures as "smart" recyclable catalyst

NASA Astrophysics Data System (ADS)

Li, Dongxiang; Liu, Na; Gao, Yuanyuan; Lin, Weihong; Li, Chunfang

2017-11-01

Core-shell AuNR@Ag nanostructures were synthesized and surface-grafted with thermosensitive poly( N-isopropylacrylamide) to enhance stability and endow stimuli-responsive property. The AuNR cores showed average dimensions of 8-nm diameter and 33-nm length, while the anisotropic silver shells displayed 1-2 nm thin side and maximal 8 nm fat side. The obtained polymer-stabilized AuNR@Ag nanostructures as catalysts showed normal Arrhenius change of apparent rate constant, k app, in catalyzed reaction between 20 and 30 °C, but displayed a decrease of k app with respect to the temperature increasing between 32.5-40 °C, showing self-inhibition of the observed catalytic activity. Such "smart" self-inhibition of catalytic activity at enhanced temperature can be attributed to the thermosensitive response of the grafted polymer molecules and should be significant to control the reaction rate and avoid superheat for exothermic reactions. Such polymer-stabilized nanocatalyst also could be recovered and reused in the catalytic system. [Figure not available: see fulltext.

In situ synchrotron XRD analysis of the kinetics of spodumene phase transitions.

PubMed

L Moore, Radhika; Mann, Jason P; Montoya, Alejandro; Haynes, Brian S

2018-04-25

The phase transition by thermal activation of natural α-spodumene was followed by in situ synchrotron XRD in the temperature range 896 to 940 °C. We observed both β- and γ-spodumene as primary products in approximately equal proportions. The rate of the α-spodumene inversion is first order and highly sensitive to temperature (apparent activation energy ∼800 kJ mol-1). The γ-spodumene product is itself metastable, forming β-spodumene, with the total product mass fraction ratio fγ/fβ decreasing as the conversion of α-spodumene continues. We found the relationship between the product yields and the degree of conversion of α-spodumene to be the same at all temperatures in the range studied. A model incorporating first order kinetics of the α- and γ-phase inversions with invariant rate constant ratio describes the results accurately. Theoretical phonon analysis of the three phases indicates that the γ phase contains crystallographic instabilities, whilst the α and β phases do not.

CO/sub 2/ absorption into aqueous MDEA and MDEA/MEA solutions

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

Critchfield, J.; Rochelle, G.T.

1987-01-01

The rate of absorption of CO/sub 2/ into 2 molal MDEA was measured by following solution composition in a stirred-cell batch reactor. The conditions investigated were 9.5 - 62/sup 0/C at a nominal CO/sub 2/ pressure of 1 atm. The data were modelled with a combined mass transfer and equilibrium model which treated the reaction of CO/sub 2/ with MDEA as second order and reversible, rather than pseudo-first order. The resulting activation energy was 13.7 kcal/gmol, and the rate constant at 30.5/sup 0/C was 4.0 (Ms)/sup -1/. The assumption of pseudo-first order conditions was found to reduce the apparent activationmore » energy to approximately 9 kcal/gmol. CO/sub 2/ absorption into 1.36 molal MDEA/0.61 molal MEA was studied at 31/sup 0/C. The experimental data were predicted better by a mass transfer model based on a shuttle mechanism than by one with two parallel reactions.« less

Template-free fabrication of hierarchical macro/mesoporpous SnS2/TiO2 composite with enhanced photocatalytic degradation of Methyl Orange (MO)

NASA Astrophysics Data System (ADS)

Dai, Gaopeng; Qin, Haiquan; Zhou, Huan; Wang, Wanqiang; Luo, Tianxiong

2018-02-01

Ordered macro/mesoporous SnS2/TiO2 composite was successfully prepared via a template-free aqueous technique using tetrabutyl titanate as the titanium precursor and SnCl4•5H2O as the tin precursor. The photocatalytic activity of SnS2/TiO2 composite was tested by the degradation of Methyl Orange (MO) aqueous solution under irradiation of the simulated sunlight. It was found that SnS2/TiO2 composite displayed an enhanced photocatalytic activity with a 0.055 min-1 apparent rate constant (degradation efficiency of 90.9% within 50 min). The ordered macro/mesoporous structure and SnS2/TiO2 heterostructure were considered to play synergistic effects in its enhanced photocatalytic performance, because the ordered porous structure can improve mass transfer and light capture, and heterostructure between SnS2 and TiO2 can reduce the recombination rate of photogenerated electrons and holes.

TiO2 Hollow Spheres: One-Pot Synthesis and Enhanced Photocatalysis

NASA Astrophysics Data System (ADS)

Jia, Changchao; Cao, Yongqiang; Yang, Ping

2013-04-01

Hollow TiO2 microspheres were successfully fabricated by metal salts with low solubility in ethanol acting as intelligent templates using a simple one-pot solvothermal method. Hollow spheres with large diameter were obtained using CuSO4ṡ5H2O as templates while small ones were obtained using Sr(NO3)2 as templates. It is found that titanium precursor plays an important role for the morphology of samples. Solid TiO2 microspheres were prepared by using titanium tetrabutoxide (TBT). In contrast, bowl-like hollow microspheres were obtained by using titanium tetrachloride (TiCl4). Furthermore, the amount of H2O can stimulate the hydrolysis rate of TiCl4 to form solid spheres. Compared with solid microspheres, hollow TiO2 microspheres depending on their interior cavity structure exhibited enhanced photocatalysis efficiency for the UV-light photodegradation of methyl orange. Quantificationally, the apparent photocatalytic degradation pseudo-first-rate constant of the hollow microspheres is 1.25 times of that of the solid ones.

The kinetics of photocatalytic degradation of aliphatic carboxylic acids in an UV/TiO2 suspension system.

PubMed

Chen, Q; Song, J M; Pan, F; Xia, F L; Yuan, J Y

2009-10-01

Kinetic studies on the photocatalytic degradation of aliphatic carboxylic acids were carried out in a slurry photoreactor with in-situ monitoring, employing artificial UV light as the source of energy and nano-TiO2 powder as the catalyst. The influences on the photocatalytic degradation such as the initial concentration of reactant (C0), catalyst dosage (CTiO2), UV intensity (Ia) and pH value have been investigated. Good agreement has been obtained between the value calculated by Langmuir-Freundlich-Hinshelwood (L-F-H) model and experimental data, with coefficient of multiple determination (R2) varying from 0.880 to 0.999. The L-F-H model has been proven to be feasible in describing the kinetic characteristic of the photocatalytic degradation of aliphatic carboxylic acids. Moreover, the apparent reaction rate constant (k) of the photocatalytic degradation of dicarboxylic acids is higher than that of monocarboxylic acids with the same carbon atoms. This shows that the photocatalytic degradation rate is favoured by different chemical structure.

Dependence of nitrite oxidation on nitrite and oxygen in low-oxygen seawater

NASA Astrophysics Data System (ADS)

Sun, Xin; Ji, Qixing; Jayakumar, Amal; Ward, Bess B.

2017-08-01

Nitrite oxidation is an essential step in transformations of fixed nitrogen. The physiology of nitrite oxidizing bacteria (NOB) implies that the rates of nitrite oxidation should be controlled by concentration of their substrate, nitrite, and the terminal electron acceptor, oxygen. The sensitivities of nitrite oxidation to oxygen and nitrite concentrations were investigated using 15N tracer incubations in the Eastern Tropical North Pacific. Nitrite stimulated nitrite oxidation under low in situ nitrite conditions, following Michaelis-Menten kinetics, indicating that nitrite was the limiting substrate. The nitrite half-saturation constant (Ks = 0.254 ± 0.161 μM) was 1-3 orders of magnitude lower than in cultivated NOB, indicating higher affinity of marine NOB for nitrite. The highest rates of nitrite oxidation were measured in the oxygen depleted zone (ODZ), and were partially inhibited by additions of oxygen. This oxygen sensitivity suggests that ODZ specialist NOB, adapted to low-oxygen conditions, are responsible for apparently anaerobic nitrite oxidation.

The vibrational dependence of dissociative recombination: Rate constants for N{sub 2}{sup +}

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

Guberman, Steven L., E-mail: slg@sci.org

Dissociative recombination rate constants are reported with electron temperature dependent uncertainties for the lowest 5 vibrational levels of the N{sub 2}{sup +} ground state. The rate constants are determined from ab initio calculations of potential curves, electronic widths, quantum defects, and cross sections. At 100 K electron temperature, the rate constants overlap with the exception of the third vibrational level. At and above 300 K, the rate constants for excited vibrational levels are significantly smaller than that for the ground level. It is shown that any experimentally determined total rate constant at 300 K electron temperature that is smaller thanmore » 2.0 × 10{sup −7} cm{sup 3}/s is likely to be for ions that have a substantially excited vibrational population. Using the vibrational level specific rate constants, the total rate constant is in very good agreement with that for an excited vibrational distribution found in a storage ring experiment. It is also shown that a prior analysis of a laser induced fluorescence experiment is quantitatively flawed due to the need to account for reactions with unknown rate constants. Two prior calculations of the dissociative recombination rate constant are shown to be inconsistent with the cross sections upon which they are based. The rate constants calculated here contribute to the resolution of a 30 year old disagreement between modeled and observed N{sub 2}{sup +} ionospheric densities.« less

Calculation of kinetic rate constants from thermodynamic data

NASA Technical Reports Server (NTRS)

Marek, C. John

1995-01-01

A new scheme for relating the absolute value for the kinetic rate constant k to the thermodynamic constant Kp is developed for gases. In this report the forward and reverse rate constants are individually related to the thermodynamic data. The kinetic rate constants computed from thermodynamics compare well with the current kinetic rate constants. This method is self consistent and does not have extensive rules. It is first demonstrated and calibrated by computing the HBr reaction from H2 and Br2. This method then is used on other reactions.

Microfluidic Platform for High-throughput Screening of Leach Chemistry.

PubMed

Yang, Die; Priest, Craig

2018-06-20

We demonstrate an optofluidic screening platform for studying thiosulfate leaching of Au in a transparent microchannel. The approach permits in situ (optical) monitoring of Au thickness, reduced reagent use, rapid optimization of reagent chem-istry, screening of temperature, and determination of the activation energy. The results demonstrate the critical importance of the (1) preparation and storage of the leach solution, (2) deposition and annealing of the Au film, and (3) lixiviant chem-istry. The density of sputter deposited Au films decreased with depth resulting in accelerating leach rates during experiments. Atomic leach rates were determined and were constant throughout each experiment. Annealing above 270 °C was found to prevent leaching, which can be attributed to diffusion of the chromium adhesion layer into the Au film. The optofluidic analysis revealed leach rates that are sensitive to the stoichiometric ratio of thiosulphate, ammonia and copper in the leach solution, and optimized for 10 mM CuSO 4 , 1 M Na 2 S 2 O 3 and 1 M NH 4 OH. The temperature dependence of the leach rate gave an apparent activation energy of ~ 40 kJ.mol -1 , based on Arrhenius' relationship.

Transient kinetic studies of pH-dependent hydrolyses by exo-type carboxypeptidase P on a 27-MHz quartz crystal microbalance.

PubMed

Furusawa, Hiroyuki; Takano, Hiroki; Okahata, Yoshio

2008-02-15

pH-Dependent kinetic parameters (k(on), k(off), and k(cat)) of protein (myoglobin) hydrolyses catalyzed by exo-enzyme (carboxypeptidase P, CPP) were obtained by using a protein-immobilized quartz crystal microbalance (QCM) in acidic aqueous solutions. The formation of the enzyme-substrate (ES) complex (k(on)), the decay of the ES complex (k(off)), and the formation of the product (k(cat)) could be analyzed by transient kinetics as mass changes on the QCM plate. The Kd (k(off)/k(on)) value was different from the Michaelis constant Km calculated from (k(off) + k(cat))/k(on) due to k(cat) > k(off). The rate-determining step was the binding step (k(on), and the catalytic rate k(cat) was faster than other k(on) and k(off) values. In the range of pH 2.5-5.0, values of k(on) gradually increased with decreasing pH showing a maximum at pH 3.7, values of k(off) were independent of pH, and k(cat) increased gradually with decreasing pH. As a result, the apparent rate constant (k(cat)/Km) showed a maximum at pH 3.7 and gradually increased with decreasing pH. The optimum pH at 3.7 of k(on) is explained by the optimum binding ability of CPP to the COOH terminus of the substrate with hydrogen bonds. The increase of k(cat) at the lower pH correlated with the decrease of alpha-helix contents of the myoglobin substrate on the QCM.

Investigation of hydrogen peroxide reduction reaction on graphene and nitrogen doped graphene nanoflakes in neutral solution

NASA Astrophysics Data System (ADS)

Amirfakhri, Seyed Javad; Binny, Dustin; Meunier, Jean-Luc; Berk, Dimitrios

2014-07-01

H2O2 reduction reaction (HPRR) is studied on both graphene (GNF) and nitrogen doped graphene nanoflakes in 0.1 M Na2SO4 solution by rotating disk electrode. The XPS results indicate that N-doped graphene nanoflakes with high nitrogen content, 32 at%N (N-GNF32), are synthesised successfully by an inductively-coupled thermal plasma (ICP) reactor. Pyridinic, pyrrolic and graphitic N species contribute up to 67% of the total nitrogen. Kinetic parameters such as Tafel slope and stoichiometric number suggest that HPRR occurs by the same mechanism on both GNF and N-GNF32. Although nitrogen does not change the mechanism of HPRR, the results indicate that the reaction rate of H2O2 reduction is enhanced on N-GNF32. The exchange current density of H2O2 reduction based on the active surface area of N-GNF32 is (8.3 ± 0.3) × 10-9 A cm-2, which is 6 times higher than the value determined for GNF. The apparent number of electrons involved in the process suggests that H2O2 decomposition competes with H2O2 reduction on both catalysts. Evaluation of the apparent heterogeneous reaction rate constant and the Tafel slope indicate that simultaneous reduction of O2 and H2O2 is negligible on the N-GNF32. On the other hand, the reduction of O2 and H2O2 occurs simultaneously on the GNF surface.

A study of estrogen metabolic clearance rates and transfer factors

PubMed Central

Hembree, W. C.; Bardin, C. W.; Lipsett, M. B.

1969-01-01

We have attempted to measure the metabolic clearance rates (MCR) and the transfer factors of estradiol (E2) and estrone (E1) during 2-hr and 12-hr infusions. When estradiol-3H was infused for 2 hr, apparent equilibrium was reached at 70 min; the 12-hr infusions showed that plasma estradiol-3H levels increased slowly throughout the infusion. When estrone-3H was infused, constancy of estrone-3H levels was not attained in either the 2-hr infusions or in the two 12-hr infusions. The tritium level in the metabolite of the infused estrogen did not become constant in 50% of the short infusions and increased during all the long infusions. Thus, the conversion ratios CE1E2 and CE2E1 continually changed and transfer factors could not be calculated. The apparent “MCR'S” calculated on the basis of the 2-hr studies expressed as liters/24 hr per m2 ±SD were: “MCRE1” (women) 980 ±94, (men) 1170 ±95; “MCRE2” (women) 615 ±17, (men) 830 ±30. The estradiol “MCR's” differed significantly between men and women. “MCRE2” was the same using either estradiol-14C or -3H and was unchanged by the infusion of 170 μg of estradiol daily. Postmenopausal women had estrogen “MCR's” in the same range as premenopausal women. Excess glucocorticoids increased the “MCRE2.” PMID:5822587

Effect of temperature and heating rate on apparent lethal concentrations of pyrolysis products

NASA Technical Reports Server (NTRS)

Hilado, C. J.; Solis, A. N.; Marcussen, W. H.; Furst, A.

1976-01-01

The apparent lethal concentrations for 50 percent of the test animals of the pyrolysis products from twelve polymeric materials were studied as a function of temperature and heating rate. The materials were polyethylene, nylon 6, ABS, polycarbonate, polyether sulfone, polyaryl sulfone, wool fabric, aromatic polyamide fabric, polychloroprene foam, polyvinyl fluoride film, Douglas fir, and red oak. The apparent lethal concentration values of most materials vary significantly with temperature and heating rate. The apparent lethal concentration values, based on weight of sample charged, appears to effectively integrate the thermophysical, thermochemical, and physiological responses from a known quantity of material under specified imposed conditions.

An experimental study on flow friction and heat transfer of water in sinusoidal wavy silicon microchannels

NASA Astrophysics Data System (ADS)

Huang, Houxue; Wu, Huiying; Zhang, Chi

2018-05-01

Sinusoidal wavy microchannels have been known as a more heat transfer efficient heat sink for the cooling of electronics than normal straight microchannels. However, the existing experimental study on wavy silicon microchannels with different phase differences are few. As a result of this, in this paper an experimental study has been conducted to investigate the single phase flow friction and heat transfer of de-ionized water in eight different sinusoidal wavy silicon microchannels (SWSMCs) and one straight silicon microchannel (SMC). The SWSMCs feature different phase differences (α  =  0 to π) and different relative wavy amplitudes (β  =  A/l  =  0.05 to 0.4), but the same average hydraulic diameters (D h  =  160 µm). It is found that both flow friction constant fRe and the Nusselt number depend on the phase difference and relative wavy amplitude. For sinusoidal wavy microchannels with a relative wavy amplitude (β  =  0.05), the Nusselt number increased noticeably with the phase difference for Re  >  250, but the effect was insignificant for Re  <  250 however, both pressure drop and apparent flow friction constant fRe increased with the increase in phase difference. For sinusoidal wavy microchannels with 0 phase difference, the increase in relative wavy amplitude obtained by reducing the wavy wave length induced higher pressure drop and apparent friction constant fRe, while the Nusselt number increased with relative wavy amplitude for Re  >  300. The results indicate that the thermal resistances of sinusoidal wavy silicon microchannels were generally lower than that of straight silicon microchannels, and the thermal resistance decreased with the increase in relative wavy amplitude. The enhancement of thermal performance is attributed to the flow re-circulation occurring in the corrugation troughs and the secondary flows or Dean vortices introduced by curved channels. It is concluded that silicon sinusoidal wavy microchannels provide higher heat transfer rate albeit with a higher flow friction, making it a better choice for the cooling of high heat flux electronics.

Long term monitoring of jaguars in the Cockscomb Basin Wildlife Sanctuary, Belize; Implications for camera trap studies of carnivores

PubMed Central

Harmsen, Bart J.; Foster, Rebecca J.; Sanchez, Emma; Gutierrez-González, Carmina E.; Silver, Scott C.; Ostro, Linde E. T.; Kelly, Marcella J.; Kay, Elma; Quigley, Howard

2017-01-01

In this study, we estimate life history parameters and abundance for a protected jaguar population using camera-trap data from a 14-year monitoring program (2002–2015) in Belize, Central America. We investigated the dynamics of this jaguar population using 3,075 detection events of 105 individual adult jaguars. Using robust design open population models, we estimated apparent survival and temporary emigration and investigated individual heterogeneity in detection rates across years. Survival probability was high and constant among the years for both sexes (φ = 0.78), and the maximum (conservative) age recorded was 14 years. Temporary emigration rate for the population was random, but constant through time at 0.20 per year. Detection probability varied between sexes, and among years and individuals. Heterogeneity in detection took the form of a dichotomy for males: those with consistently high detection rates, and those with low, sporadic detection rates, suggesting a relatively stable population of ‘residents’ consistently present and a fluctuating layer of ‘transients’. Female detection was always low and sporadic. On average, twice as many males than females were detected per survey, and individual detection rates were significantly higher for males. We attribute sex-based differences in detection to biases resulting from social variation in trail-walking behaviour. The number of individual females detected increased when the survey period was extended from 3 months to a full year. Due to the low detection rates of females and the variable ‘transient’ male subpopulation, annual abundance estimates based on 3-month surveys had low precision. To estimate survival and monitor population changes in elusive, wide-ranging, low-density species, we recommend repeated surveys over multiple years; and suggest that continuous monitoring over multiple years yields even further insight into population dynamics of elusive predator populations. PMID:28658274

Improved resolution of single channel dwell times reveals mechanisms of binding, priming, and gating in muscle AChR

PubMed Central

Mukhtasimova, Nuriya; daCosta, Corrie J.B.

2016-01-01

The acetylcholine receptor (AChR) from vertebrate skeletal muscle initiates voluntary movement, and its kinetics of activation are crucial for maintaining the safety margin for neuromuscular transmission. Furthermore, the kinetic mechanism of the muscle AChR serves as an archetype for understanding activation mechanisms of related receptors from the Cys-loop superfamily. Here we record currents through single muscle AChR channels with improved temporal resolution approaching half an order of magnitude over our previous best. A range of concentrations of full and partial agonists are used to elicit currents from human wild-type and gain-of-function mutant AChRs. For each agonist–receptor combination, rate constants are estimated from maximum likelihood analysis using a kinetic scheme comprised of agonist binding, priming, and channel gating steps. The kinetic scheme and rate constants are tested by stochastic simulation, followed by incorporation of the experimental step response, sampling rate, background noise, and filter bandwidth. Analyses of the simulated data confirm all rate constants except those for channel gating, which are overestimated because of the established effect of noise on the briefest dwell times. Estimates of the gating rate constants were obtained through iterative simulation followed by kinetic fitting. The results reveal that the agonist association rate constants are independent of agonist occupancy but depend on receptor state, whereas those for agonist dissociation depend on occupancy but not on state. The priming rate and equilibrium constants increase with successive agonist occupancy, and for a full agonist, the forward rate constant increases more than the equilibrium constant; for a partial agonist, the forward rate and equilibrium constants increase equally. The gating rate and equilibrium constants also increase with successive agonist occupancy, but unlike priming, the equilibrium constants increase more than the forward rate constants. As observed for a full and a partial agonist, the gain-of-function mutation affects the relationship between rate and equilibrium constants for priming but not for channel gating. Thus, resolving brief single channel currents distinguishes priming from gating steps and reveals how the corresponding rate and equilibrium constants depend on agonist occupancy. PMID:27353445

The biogeochemical effect of seaweeds upon close-to natural concentrations of dissolved iodate and iodide in seawater Preliminary study with Laminaria digitata and Fucus serratus

NASA Astrophysics Data System (ADS)

Truesdale, Victor W.

2008-06-01

Toward assessing the biogeochemical significance of seaweeds in relation to dissolved iodine in seawater, the effect of whole seaweeds ( Laminaria digitata and Fucus serratus) upon iodide and iodate, at essentially natural concentrations, has been studied. The weeds were carefully removed from the sub-littoral zone of the Menai Straits and exposed to iodide and iodate at their natural temperature (6 °C), but under continuous illumination. Laminaria digitata was found to decrease the concentration of iodate with an exponential rate constant of 0.008-0.24 h -1. This is a newly discovered process which, if substantiated, will require an entirely new mechanism. Generally, apparent iodide concentration increased except in a run with seawater augmented with iodide, where it first decreased. The rate constant for loss of iodide was 0.014-0.16 h -1. Meanwhile, F. serratus was found not to decrease iodate concentrations, as did L. digitata. Indeed, after ˜30 h iodate concentrations increased, suggesting that the weed may take in iodide before oxidising and releasing it. If substantiated, this finding may offer a way into one of the most elusive of processes within the iodine cycle - iodide oxidation. With both seaweeds sustained long-term increases of apparent iodide concentration are most easily explained as a secretion by the weeds of organic matter which is capable of reducing the Ce(IV) reagent used in determination of total iodine. Modelling of the catalytic method used is provided to support this contention. The possibility of developing this to measure the strain that seaweeds endure in this kind of biogeochemical flux experiment is discussed. A Chemical Oxygen Demand type of approach is applied using Ce(IV) as oxidant. The results of the iodine experiments are contrasted with the several investigations of 131I interaction with seaweeds, which have routinely used discs of weed cut from the frond. It is argued that experiments conducted with stable iodine may measure a different variable to that measured in radio-iodine experiments.

A kinetic model for beta-amyloid adsorption at the air/solution interface and its implication to the beta-amyloid aggregation process.

PubMed

Jiang, Dianlu; Dinh, Kim Lien; Ruthenburg, Travis C; Zhang, Yi; Su, Lei; Land, Donald P; Zhou, Feimeng

2009-03-12

At the air/buffer solution interface the kinetics of adsorption of amyloid beta peptide, Abeta(1-42), whose bulk concentration (submicromolar) is more than 2 orders of magnitude lower than that typically used in other in vitro aggregation studies, has been studied using a Langmuir-Blodgett trough. The pressure-time curves exhibit a lag phase, wherein the surface pressure essentially remains at zero, and a rising phase, corresponding to the Abeta adsorption at the interface. The duration of the lag phase was found to be highly dependent on both the Abeta bulk concentration and the solution temperature. A large activation energy (62.2 +/- 4.1 KJ/mol) was determined and the apparent adsorption rate constant was found to be linearly dependent on the Abeta bulk concentration. Attenuated total reflection-IR spectra of the adsorbed Abeta transferred to a solid substrate and circular dichroism measurements of Abeta in the solution layer near the interface reveal that the natively unstructured Abeta in the bulk undergo a conformation change (folding) to mainly the alpha-helical structure. The results suggest that, prior to the adsorption step, an equilibrium between Abeta conformations is established within the subsurface. The kinetic equation derived from this model confirms that the overall Abeta adsorption is kinetically controlled and the apparent rate constant is proportional to the Abeta bulk concentration. This model also indicates that interfaces such as cell membranes and lipid bilayers may facilitate Abeta aggregation/ fibrillation by providing a thin hydrophobic layer adjacent to the interface for the initial A/beta conformation change (misfolding) and accumulation. Such a preconcentration effect offers a plausible explanation of the fact that Abeta fibrillation occurs in vivo at nanomolar concentrations. Another important biological implication from our work is that Abeta misfolding may occur before its adsorption onto a cell membrane. This general kinetic model should also find applications in adsorption studies of other types of biomolecules whose overall kinetics exhibits a lag phase that is dependent on the bulk concentration of the adsorbate.

Reaction of cytochrome c with nitrite and nitric oxide. A model of dissimilatory nitrite reductase.

PubMed

Orii, Y; Shimada, H

1978-12-01

The reaction of bovine heart ferrocytochrome c with nitrite was studied under various conditions. The reaction product was ferricytochrome c at around pH 5, whereas at around pH 3 it was Compound I, characterized by twin peaks at 529 and 563 nm of equal intensity. However, ferrocytochrome c decreased obeying first-order kinetics over the pH range examined, irrespective of the presence or absence of molecular oxygen. The apparent first-order rate constant was proportional to the square of the nitrite concentration at pH 4.4 and it increased as the pH was lowered. At pH 3 the reaction was so rapid that it had to be followed by stopped-flow and rapid-scanning techniques. The apparent rate constant at this pH was found to increase linearly with the nitrite concentration. Based on these results the active species of nitrite was concluded to be dinitrogen trioxide at pH 4.4 and nitrosonium ion, no+, at pH 3. Compound II was formed by reaction of ferrocytochrome c and NO gas at acidic and alkaline pH values. The absorption peaks were at 533 and 563 nm at pH 3, and at 538 and 567 nm at pH 12.9. This compound was also formed by reducing Compound I with reductants. Compound I prepared from ferricytochrome c and NO was stable below pH 6. However, appreciable absorption peaks for ferrocytochrome c appeared between pH 8 and 10, because Compound I was dissociated into ferrocytochrome c and NO+, and because ferrocytochrome c thus formed reacted with NO very slowly in this pH region. Saccharomyces ferricytochrome c under NO gas behaved differently from mammalian cytochrome, indicating the significance of the nature of the heme environment in determing the reactivity. Only at extreme pH values was Compound II formed exclusively and persisted. A model system for dissimilatory nitrite reductase was constructed by using bovine heart cytochrome c, nitrite and NADH plus PMS at pH 3.3, and a scheme involving cyclic turnover of ferrocytochrome c, Compound I and Compound II is presented, with kinetic parameters.

A Kinetic Model for β-Amyloid Adsorption at the Air/Solution Interface and Its Implication to the β-Amyloid Aggregation Process

PubMed Central

Jiang, Dianlu; Dinh, Kim Lien; Ruthenburg, Travis; Zhang, Yi; Su, Lei; Land, Donald; Zhou, Feimeng

2011-01-01

The kinetics of adsorption at the air/buffer solution interface of amyloid beta peptide, Aβ(1–42), whose bulk concentration (submicromolar) is more than two orders of magnitude lower than that typically used in other in vitro aggregation studies, has been studied using a Langmuir-Blodgett trough. The pressure–time curves exhibit a lag phase, wherein the surface pressure essentially remains at zero, and a rising phase, corresponding to the Aβ adsorption at the interface. The duration of the lag phase was found to be highly dependent on both the Aβ bulk concentration and the solution temperature. A large activation energy (62.2 ± 4.1 KJ/mol) was determined and the apparent adsorption rate constant was found to be linearly dependent on the Aβ bulk concentration. Attenuated total reflection-IR spectra of the adsorbed Aβ transferred to a solid substrate and circular dichroism measurements of Aβ in the solution layer near the interface reveal that the natively unstructured Aβ in the bulk undergo a conformation change (folding) to mainly the α-helical structure. The results suggest that, prior to the adsorption step, an equilibrium between Aβ conformations is established within the subsurface. The kinetic equation derived from this model confirms that the overall Aβ adsorption is kinetically controlled and the apparent rate constant is proportional to the Aβ bulk concentration. This model also indicates that interfaces such as cell membranes and lipid bilayers may facilitate Aβ aggregation/fibrillation by providing a thin hydrophobic layer adjacent to the interface for the initial Aβ conformation change (misfolding) and accumulation. Such a preconcentration effect offers a plausible explanation of the fact that Aβ fibrillation occurs in vivo at nanomolar concentrations. Another important biological implication from our work is that Aβ misfolding may occur before its adsorption onto a cell membrane. This general kinetic model should also find applications in adsorption studies of other types of biomolecules whose overall kinetics exhibits a lag phase that is dependent on the bulk concentration of the adsorbate. PMID:19260715

Effect of environmental factors on the kinetics of insulin fibril formation: elucidation of the molecular mechanism.

PubMed

Nielsen, L; Khurana, R; Coats, A; Frokjaer, S; Brange, J; Vyas, S; Uversky, V N; Fink, A L

2001-05-22

In the search for the molecular mechanism of insulin fibrillation, the kinetics of insulin fibril formation were studied under different conditions using the fluorescent dye thioflavin T (ThT). The effect of insulin concentration, agitation, pH, ionic strength, anions, seeding, and addition of 1-anilinonaphthalene-8-sulfonic acid (ANS), urea, TMAO, sucrose, and ThT on the kinetics of fibrillation was investigated. The kinetics of the fibrillation process could be described by the lag time for formation of stable nuclei (nucleation) and the apparent rate constant for the growth of fibrils (elongation). The addition of seeds eliminated the lag phase. An increase in insulin concentration resulted in shorter lag times and faster growth of fibrils. Shorter lag times and faster growth of fibrils were seen at acidic pH versus neutral pH, whereas an increase in ionic strength resulted in shorter lag times and slower growth of fibrils. There was no clear correlation between the rate of fibril elongation and ionic strength. Agitation during fibril formation attenuated the effects of insulin concentration and ionic strength on both lag times and fibril growth. The addition of ANS increased the lag time and decreased the apparent growth rate for insulin fibril formation. The ANS-induced inhibition appears to reflect the formation of amorphous aggregates. The denaturant, urea, decreased the lag time, whereas the stabilizers, trimethylamine N-oxide dihydrate (TMAO) and sucrose, increased the lag times. The results indicated that both nucleation and fibril growth were controlled by hydrophobic and electrostatic interactions. A kinetic model, involving the association of monomeric partially folded intermediates, whose concentration is stimulated by the air-water interface, leading to formation of the critical nucleus and thence fibrils, is proposed.

Relationship of compressive stress-strain response of engineering materials obtained at constant engineering and true strain rates

DOE PAGES

Song, Bo; Sanborn, Brett

2018-05-07

In this paper, a Johnson–Cook model was used as an example to analyze the relationship of compressive stress-strain response of engineering materials experimentally obtained at constant engineering and true strain rates. There was a minimal deviation between the stress-strain curves obtained at the same constant engineering and true strain rates. The stress-strain curves obtained at either constant engineering or true strain rates could be converted from one to the other, which both represented the intrinsic material response. There is no need to specify the testing requirement of constant engineering or true strain rates for material property characterization, provided that eithermore » constant engineering or constant true strain rate is attained during the experiment.« less

Relationship of compressive stress-strain response of engineering materials obtained at constant engineering and true strain rates

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

Song, Bo; Sanborn, Brett

In this paper, a Johnson–Cook model was used as an example to analyze the relationship of compressive stress-strain response of engineering materials experimentally obtained at constant engineering and true strain rates. There was a minimal deviation between the stress-strain curves obtained at the same constant engineering and true strain rates. The stress-strain curves obtained at either constant engineering or true strain rates could be converted from one to the other, which both represented the intrinsic material response. There is no need to specify the testing requirement of constant engineering or true strain rates for material property characterization, provided that eithermore » constant engineering or constant true strain rate is attained during the experiment.« less

Catalytic properties and heat stabilities of novel recombinant human N-acetyltransferase 2 allozymes support existence of genetic heterogeneity within the slow acetylator phenotype.

PubMed

Hein, David W; Doll, Mark A

2017-08-01

Human N-acetyltransferase 2 (NAT2) catalyzes the N-acetylation of numerous aromatic amine drugs such as sulfamethazine (SMZ) and hydrazine drugs such as isoniazid (INH). NAT2 also catalyzes the N-acetylation of aromatic amine carcinogens such as 2-aminofluorene and the O- and N,O-acetylation of aromatic amine and heterocyclic amine metabolites. Genetic polymorphism in NAT2 modifies drug efficacy and toxicity as well as cancer risk. Acetyltransferase catalytic activities and heat stability associated with six novel NAT2 haplotypes (NAT2*6C, NAT2*14C, NAT2*14D, NAT2*14E, NAT2*17, and NAT2*18) were compared with that of the reference NAT2*4 haplotype following recombinant expression in Escherichia coli. N-acetyltransferase activities towards SMZ and INH were significantly (p < 0.0001) lower when catalyzed by the novel recombinant human NAT2 allozymes compared to NAT2 4. SMZ and INH N-acetyltransferase activities catalyzed by NAT2 14C and NAT2 14D were significantly lower (p < 0.001) than catalyzed by NAT2 6C and NAT2 14E. N-Acetylation catalyzed by recombinant human NAT2 17 was over several hundred-fold lower than by recombinant NAT2 4 precluding measurement of its kinetic or heat inactivation constants. Similar results were observed for the O-acetylation of N-hydroxy-2-aminofluorene and N-hydroxy-2-amino-1-methyl-6-phenylimidazo [4,5-b] pyridine and the intramolecular N,O-acetylation of N-hydroxy-N-acetyl-2-aminofluorene. The apparent V max of the novel recombinant NAT2 allozymes NAT2 6C, NAT2 14C, NAT2 14D, and NAT2 14E towards AF, 4-aminobiphenyl (ABP), and 3,2'-dimethyl-4-aminobiphenyl (DMABP) were each significantly (p < 0.001) lower while their apparent K m values did not differ significantly (p > 0.05) from recombinant NAT2 4. The apparent V max catalyzed by NAT2 14C and NAT2 14D were significantly lower (p < 0.05) than the apparent V max catalyzed by NAT2 6C and NAT2 14E towards AF, ABP, and DMABP. Heat inactivation rate constants for recombinant human NAT2 14C, 14D, 14E, and 18 were significantly (p < 0.05) higher than NAT2 4. These results provide further evidence of genetic heterogeneity within the NAT2 slow acetylator phenotype.

Comparison of TID Effects in Space-Like Variable Dose Rates and Constant Dose Rates

NASA Technical Reports Server (NTRS)

Harris, Richard D.; McClure, Steven S.; Rax, Bernard G.; Evans, Robin W.; Jun, Insoo

2008-01-01

The degradation of the LM193 dual voltage comparator has been studied at different TID dose rate profiles, including several different constant dose rates and a variable dose rate that simulates the behavior of a solar flare. A comparison of results following constant dose rate vs. variable dose rates is made to explore how well the constant dose rates used for typical part testing predict the performance during a simulated space-like mission. Testing at a constant dose rate equal to the lowest dose rate seen during the simulated flare provides an extremely conservative estimate of the overall amount of degradation. A constant dose rate equal to the average dose rate is also more conservative than the variable rate. It appears that, for this part, weighting the dose rates by the amount of total dose received at each rate (rather than the amount of time at each dose rate) results in an average rate that produces an amount of degradation that is a reasonable approximation to that received by the variable rate.

Hydrothermal Preparation and Characterization of Ultralong Strontium-Substituted Hydroxyapatite Whiskers Using Acetamide as Homogeneous Precipitation Reagent

PubMed Central

Xu, Jianqiang; Yang, Yaoqi; Wan, Rong; Zhang, Weibin

2014-01-01

The ultralong strontium- (Sr-) substituted hydroxyapatite (SrHAp) whiskers were successfully prepared using acetamide as homogeneous precipitation reagent. The effect of the Sr substitution amount on the lattice constants and proliferation of human osteoblast cells (MG-63) was further investigated. The results showed that the SrHAp whiskers with diameter of 0.2–12 μm and ultralong length up to 200 μm were obtained and the Sr substitution level could be facilely tailored by regulating the initial molar ratio of Sr/(Sr + Ca) in raw materials. The Sr2+ replaced part of Ca2+ and the lattice constants increased apparently with the increase of the Sr substitution amount. Compared with the pure HAp whiskers, the Sr substitution apparently stimulated the proliferation of MG-63 at certain extracted concentrations. Our study suggested that the obtained SrHAp whiskers might be used as bioactive and mechanical reinforcement materials for hard tissue regeneration applications. PMID:24592192

Fulvic acid-sulfide ion competition for mercury ion binding in the Florida everglades

USGS Publications Warehouse

Reddy, M.M.; Aiken, G.R.

2001-01-01

Negatively charged functional groups of fulvic acid compete with inorganic sulfide ion for mercury ion binding. This competition is evaluated here by using a discrete site-electrostatic model to calculate mercury solution speciation in the presence of fulvic acid. Model calculated species distributions are used to estimate a mercury-fulvic acid apparent binding constant to quantify fulvic acid and sulfide ion competition for dissolved inorganic mercury (Hg(II)) ion binding. Speciation calculations done with PHREEQC, modified to use the estimated mercury-fulvic acid apparent binding constant, suggest that mercury-fulvic acid and mercury-sulfide complex concentrations are equivalent for very low sulfide ion concentrations (about 10-11 M) in Everglades' surface water. Where measurable total sulfide concentration (about 10-7 M or greater) is present in Everglades' surface water, mercury-sulfide complexes should dominate dissolved inorganic mercury solution speciation. In the absence of sulfide ion (for example, in oxygenated Everglades' surface water), fulvic acid binding should dominate Everglades' dissolved inorganic mercury speciation.

Measurements of dispersion forces between colloidal latex particles with the atomic force microscope and comparison with Lifshitz theory

NASA Astrophysics Data System (ADS)

Elzbieciak-Wodka, Magdalena; Popescu, Mihail N.; Ruiz-Cabello, F. Javier Montes; Trefalt, Gregor; Maroni, Plinio; Borkovec, Michal

2014-03-01

Interaction forces between carboxylate colloidal latex particles of about 2 μm in diameter immersed in aqueous solutions of monovalent salts were measured with the colloidal probe technique, which is based on the atomic force microscope. We have systematically varied the ionic strength, the type of salt, and also the surface charge densities of the particles through changes in the solution pH. Based on these measurements, we have accurately measured the dispersion forces acting between the particles and estimated the apparent Hamaker constant to be (2.0 ± 0.5) × 10-21 J at a separation distance of about 10 nm. This value is basically independent of the salt concentration and the type of salt. Good agreement with Lifshitz theory is found when roughness effects are taken into account. The combination of retardation and roughness effects reduces the value of the apparent Hamaker constant and its ionic strength dependence with respect to the case of ideally smooth surfaces.

Measurements of dispersion forces between colloidal latex particles with the atomic force microscope and comparison with Lifshitz theory.

PubMed

Elzbieciak-Wodka, Magdalena; Popescu, Mihail N; Montes Ruiz-Cabello, F Javier; Trefalt, Gregor; Maroni, Plinio; Borkovec, Michal

2014-03-14

Interaction forces between carboxylate colloidal latex particles of about 2 μm in diameter immersed in aqueous solutions of monovalent salts were measured with the colloidal probe technique, which is based on the atomic force microscope. We have systematically varied the ionic strength, the type of salt, and also the surface charge densities of the particles through changes in the solution pH. Based on these measurements, we have accurately measured the dispersion forces acting between the particles and estimated the apparent Hamaker constant to be (2.0 ± 0.5) × 10(-21) J at a separation distance of about 10 nm. This value is basically independent of the salt concentration and the type of salt. Good agreement with Lifshitz theory is found when roughness effects are taken into account. The combination of retardation and roughness effects reduces the value of the apparent Hamaker constant and its ionic strength dependence with respect to the case of ideally smooth surfaces.

Volumetric and acoustical behaviour of sodium saccharin in aqueous system over temperature range (20.0-45.0)°C.

PubMed

Jamal, Muhammad Asghar; Rashad, Muhammad; Khosa, Muhammad Kaleem; Bhatti, Haq Nawaz

2015-04-15

Densities and ultrasonic velocity values for aqueous solutions of sodium saccharin (SS) has been measured as a function of concentration at 20.0-45.0 °C and atmospheric pressure using DSA-5000 M. The density and ultrasonic velocity values have been further used to calculate apparent molar volume, apparent specific volume, isentropic apparent molar compressibility and compressibility hydration numbers and reported. The values for apparent molar volume obtained at given temperatures showed negative deviations from Debye-Hückel limiting law and used as a direct measure of the ion-ion and ion-solvent interactions. The apparent specific volumes of the solute were calculated and it was found that these values of the investigated solutions lie on the borderline between the values reported for sweet substances. The sweetness response of the sweeteners is then explained in terms of their solution behaviours. Furthermore, the partial molar expansibility, its second derivative, (∂(2)V°/∂T(2)) as Hepler's constant and thermal expansion coefficient have been estimated. Copyright © 2014 Elsevier Ltd. All rights reserved.

Dynamics of protozoa in the rumen of cattle.

PubMed

Ffoulkes, D; Leng, R A

1988-05-01

1. The dynamics of protozoa were studied in two groups of rumen-fistulated cattle fed on a basal diet of molasses ad lib., with oaten chaff given at 6 or 18 g/kg live weight. This diet resulted in different mixtures of protozoal species in the populations in the rumen. 2. The rumen protozoa were studied by intrarumen injections of protozoa labelled in vitro with [14CH3]choline. An indication of protozoal death and fermentation of protozoal cell residues was obtained by measuring 14C loss via the methane pool. 3. After a single injection of labelled protozoa, the decline in the specific radioactivity (microCi/g nitrogen) of the protozoal pool in the rumen indicated that first-order kinetic processes applied. Conversely the specific radioactivity of protozoa, incubated in rumen fluid, remained constant indicating no growth in vitro, presumably owing to a rapid exhaustion of essential nutrients. 4. The protozoal populations in the rumen of cattle fed on the diet with the low level of oaten chaff were mainly small ciliates; but on the higher level of chaff in the diet, the large ciliates were a higher proportion of the total protozoal population present. 5. The mean pool size of protozoa in the rumen was significantly larger and the protozoal half-life tended to be longer for cattle fed on the higher level of chaff in the diet. The apparent production rate of protozoa in cattle fed on each diet was not significantly different and there were no differences in the production rate of methane. The percentage losses of label from protozoa in the rumen via the methane pool were not significantly different on the two diets and indicated that 74% of the protozoa that were apparently irreversibly lost from the rumen could be accounted for by death and lysis in the rumen and therefore only 26% of protozoa apparently entered the lower digestive tract.

Application of the compensated Arrhenius formalism to explain the dielectric constant dependence of rates for Menschutkin reactions.

PubMed

Petrowsky, Matt; Glatzhofer, Daniel T; Frech, Roger

2013-11-21

The dependence of the reaction rate on solvent dielectric constant is examined for the reaction of trihexylamine with 1-bromohexane in a series of 2-ketones over the temperature range 25-80 °C. The rate constant data are analyzed using the compensated Arrhenius formalism (CAF), where the rate constant assumes an Arrhenius-like equation that also contains a dielectric constant dependence in the exponential prefactor. The CAF activation energies are substantially higher than those obtained using the simple Arrhenius equation. A master curve of the data is observed by plotting the prefactors against the solvent dielectric constant. The master curve shows that the reaction rate has a weak dependence on dielectric constant for values approximately less than 10 and increases more rapidly for dielectric constant values greater than 10.

Rate constants for proteins binding to substrates with multiple binding sites using a generalized forward flux sampling expression

NASA Astrophysics Data System (ADS)

Vijaykumar, Adithya; ten Wolde, Pieter Rein; Bolhuis, Peter G.

2018-03-01

To predict the response of a biochemical system, knowledge of the intrinsic and effective rate constants of proteins is crucial. The experimentally accessible effective rate constant for association can be decomposed in a diffusion-limited rate at which proteins come into contact and an intrinsic association rate at which the proteins in contact truly bind. Reversely, when dissociating, bound proteins first separate into a contact pair with an intrinsic dissociation rate, before moving away by diffusion. While microscopic expressions exist that enable the calculation of the intrinsic and effective rate constants by conducting a single rare event simulation of the protein dissociation reaction, these expressions are only valid when the substrate has just one binding site. If the substrate has multiple binding sites, a bound enzyme can, besides dissociating into the bulk, also hop to another binding site. Calculating transition rate constants between multiple states with forward flux sampling requires a generalized rate expression. We present this expression here and use it to derive explicit expressions for all intrinsic and effective rate constants involving binding to multiple states, including rebinding. We illustrate our approach by computing the intrinsic and effective association, dissociation, and hopping rate constants for a system in which a patchy particle model enzyme binds to a substrate with two binding sites. We find that these rate constants increase as a function of the rotational diffusion constant of the particles. The hopping rate constant decreases as a function of the distance between the binding sites. Finally, we find that blocking one of the binding sites enhances both association and dissociation rate constants. Our approach and results are important for understanding and modeling association reactions in enzyme-substrate systems and other patchy particle systems and open the way for large multiscale simulations of such systems.

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

Saha, J.; Chaudhary, S.; Majumdar, P.

We report a study on potential multiferroic characteristics of Yttrium Iron Garnet (YIG). The emergence of ferroelectricity in YIG is in debate but we provide evidence for strong magneto-electric coupling above room temperature from dielectric constant measurement with and without magnetic field. We find that the apparent pseudo-ferroelectric crossover temperature in YIG varies with frequency. For higher frequency the transition shifts towards higher temperature. This is indicative of relaxor behavior. We have also measured the dielectric constant in the presence of external magnetic field at high temperature that confirms interdependence of magnetic and dielectric properties.

Determination of ionization constants by paper electrophoresis.

PubMed Central

Tate, M E

1981-01-01

Dimensionless apparent ionization constants of charged low-molecular-weight species may be obtained from paper-electrophoretic data at 20-25 degrees C with buffers (I0.1-0.5) of measured pH (1.5-12.5) containing oxalate ions. Relative mobilities rather than absolute mobilities were measured by using glycerol and m-nitrobenzenesulphonate respectively as standards of zero and unit mobility. Application of the procedure to ionizations of adenine, adenosine, 2'-deoxyadenosine, 3'-deoxyadenosine, 3':5'-cyclic AMP, ADP, ADP-glucose-agrocin 84 and ATP is described. PMID:6976169

Comminution of solids caused by kinetic energy of high shear strain rate, with implications for impact, shock, and shale fracturing

PubMed Central

Bažant, Zdeněk P.; Caner, Ferhun C.

2013-01-01

Although there exists a vast literature on the dynamic comminution or fragmentation of rocks, concrete, metals, and ceramics, none of the known models suffices for macroscopic dynamic finite element analysis. This paper outlines the basic idea of the macroscopic model. Unlike static fracture, in which the driving force is the release of strain energy, here the essential idea is that the driving force of comminution under high-rate compression is the release of the local kinetic energy of shear strain rate. The density of this energy at strain rates >1,000/s is found to exceed the maximum possible strain energy density by orders of magnitude, making the strain energy irrelevant. It is shown that particle size is proportional to the −2/3 power of the shear strain rate and the 2/3 power of the interface fracture energy or interface shear stress, and that the comminution process is macroscopically equivalent to an apparent shear viscosity that is proportional (at constant interface stress) to the −1/3 power of this rate. A dimensionless indicator of the comminution intensity is formulated. The theory was inspired by noting that the local kinetic energy of shear strain rate plays a role analogous to the local kinetic energy of eddies in turbulent flow. PMID:24218624

Rate constants measured for hydrated electron reactions with peptides and proteins

NASA Technical Reports Server (NTRS)

Braams, R.

1968-01-01

Effects of ionizing radiation on the amino acids of proteins and the reactivity of the protonated amino group depends upon the pK subscript a of the group. Estimates of the rate constants for reactions involving the amino acid side chains are presented. These rate constants gave an approximate rate constant for three different protein molecules.

Solvation and Acid Strength Effects on Catalysis by Faujasite Zeolites

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

Gounder, Rajamani P.; Jones, Andrew J.; Carr, Robert T.

2012-02-01

Kinetic, spectroscopic, and chemical titration data indicate that differences in monomolecular isobutane cracking and dehydrogenation and methanol dehydration turnover rates (per H+) among FAU zeolites treated thermally with steam (H-USY) and then chemically with ammonium hexafluorosilicate (CDHUSY) predominantly reflect differences in the size and solvating properties of their supercage voids rather than differences in acid strength. The number of protons on a given sample was measured consistently by titrations with Na+, with CH3 groups via reactions of dimethyl ether, and with 2,6-di-tert-butylpyridine during methanol dehydration catalysis; these titration values were also supported by commensurate changes in acidic OH infrared bandmore » areas upon exposure to titrant molecules. The number of protons, taken as the average of the three titration methods, was significantly smaller than the number of framework Al atoms (Alf) obtained from X-ray diffraction and 27Al magic angle spinning nuclear magnetic resonance spectroscopy on H-USY (0.35 H+/Alf) and CD-HUSY (0.69 H+/Alf). These data demonstrate that the ubiquitous use of Alf sites as structural proxies for active H+ sites in zeolites can be imprecise, apparently because distorted Al structures that are not associated with acidic protons are sometimes detected as Alf sites. Monomolecular isobutane cracking and dehydrogenation rate constants, normalized non-rigorously by the number of Alf species, decreased with increasing Na+ content on both H-USY and CD-HUSY samples and became undetectable at sub-stoichiometric exchange levels (0.32 and 0.72 Na+/Alf ratios, respectively), an unexpected finding attributed incorrectly in previous studies to the presence of minority ‘‘super-acidic’’ sites. These rate constants, when normalized rigorously by the number of residual H+ sites were independent of Na+ content on both H-USY and CD-HUSY samples, reflecting the stoichiometric replacement of protons that are uniform in reactivity by Na+ cations. Monomolecular isobutane cracking and dehydrogenation rate constants (per H+; 763 K), however, were higher on H-USY than CD-HUSY (by a factor of 1.4). Equilibrium constants for the formation of protonated methanol dimers via adsorption of gaseous methanol onto adsorbed methanol monomers, determined from kinetic studies of methanol dehydration to dimethyl ether (433 K), were also higher on H-USY than CD-HUSY (by a factor of 2.1). These larger constants predominantly reflect stronger dispersive interactions in H-USY, consistent with its smaller supercage voids that result from the occlusion of void space by extraframework Al (Alex) residues. These findings appear to clarify enduring controversies about the mechanistic interpretation of the effects of Na+ and Alex species on the catalytic reactivity of FAU zeolites. They also illustrate the need to normalize rates by the number of active sites instead of more convenient but less accurate structural proxies for such sites.« less

Influence of ablation impurities on blunt body re-entry ionization

NASA Technical Reports Server (NTRS)

Schexnayder, C. J., Jr.; Evans, J. S.

1974-01-01

Electron density profiles which include the effect of an ablated sodium impurity were computed for the boundary layer on a blunt-nosed body re-entering the atmosphere at 7.62 km/sec. Profiles are computed from the nose to a distance of four diameters along the RAM C-payload. A finite-difference, laminar, nonequilibrium chemistry boundary-layer program was used. Comparison of theory with S-band diagnostic antenna results, electron concentration deduced from X- and C-band attenuation data, and Langmuir probe data at several different aft body locations show that agreement is good at high altitude. At the lower altitudes there is disagreement between theory and S-band antenna data where the apparent discrepancy is attributed to the three-body recombination rate constant used for deionization of sodium coupled with the effect of angle of attack.

Respiratory enzymes of Thiobacillus ferrooxidans. Kinetic properties of an acid-stable iron:rusticyanin oxidoreductase.

PubMed

Blake, R C; Shute, E A

1994-08-09

Rusticyanin is an acid-stable, soluble blue copper protein found in abundance in the periplasmic space of Thiobacillus ferrooxidans, an acidophilic bacterium capable of growing autotrophically on soluble ferrous sulfate. An acid-stable iron:rusticyanin oxidoreductase activity was partially purified from cell-free extracts of T. ferrooxidans. The enzyme-catalyzed, iron-dependent reduction of the rusticyanin exhibited three kinetic properties characteristic of aerobic iron oxidation by whole cells. (i) A survey of 14 different anions indicated that catalysis by the oxidoreductase occurred only in the presence of sulfate or selenate, an anion specificity identical to that of whole cells. (ii) Saturation with both sulfatoiron(II) and the catalyst produced a concentration-independent rate constant of 3 s-1 for the reduction of the rusticyanin, which is an electron transfer reaction sufficiently rapid to account for the flux of electrons through the iron respiratory chain. (iii) Values for the enzyme-catalyzed pseudo-first-order rate constants for the reduction of the rusticyanin showed a hyperbolic dependence on the concentration of sulfatoiron(II) with a half-maximal effect at 300 microM, a value similar to the apparent KM for iron shown by whole cells. On the basis of these favorable comparisons between the behavior patterns of isolated biomolecules and those of whole cells, this iron:rusticyanin oxidoreductase is postulated to be the primary cellular oxidant of ferrous ions in the iron respiratory electron transport chain of T. ferrooxidans.

A novel nitromethane biosensor based on biocompatible conductive redox graphene-chitosan/hemoglobin/graphene/room temperature ionic liquid matrix.

PubMed

Wang, Lu; Zhang, Xiuhua; Xiong, Huayu; Wang, Shengfu

2010-11-15

A novel amperometric biosensor for nitromethane (CH(3)NO(2)) based on immobilization of graphene (GR), chitosan (CS), hemoglobin (Hb) and room temperature ionic liquid (IL) on a glassy carbon electrode (GCE) was developed for the first time. The surface morphologies of a set of representative membranes were characterized by means of scanning electron microscopy (SEM). The electrochemical performance of the biosensor was evaluated by cyclic voltammetry (CV) and chronoamperometry. A pair of stable and well-defined redox peaks of Hb with a formal potential of -0.240 V was observed at the GR-CS/Hb/GR/IL/GCE. The effects of phosphate buffer pH, scan rate, and temperature on the biosensor were investigated to provide optimum analytical performance. Moreover, several electrochemical parameters, e.g., the heterogeneous electron transfer rate constant (k(s)), were calculated in detail. The presence of both GR and IL not only dramatically facilitated the electron transfer of Hb, but also greatly enhanced electrocatalytic activity towards CH(3)NO(2). The apparent Michaelis-Menten constant was down to 0.16 μM, indicating that the biosensor possessed high affinity to CH(3)NO(2). Besides this, the proposed biosensor exhibited fast amperometric response (<5s), low detection limit (6.0 × 10(-10)M), and excellent long-time storage stability for the determination of CH(3)NO(2). Copyright © 2010 Elsevier B.V. All rights reserved.

Oxidation of indometacin by ferrate (VI): kinetics, degradation pathways, and toxicity assessment.

PubMed

Huang, Junlei; Wang, Yahui; Liu, Guoguang; Chen, Ping; Wang, Fengliang; Ma, Jingshuai; Li, Fuhua; Liu, Haijin; Lv, Wenying

2017-04-01

The oxidation of indometacin (IDM) by ferrate(VI) (Fe(VI)) was investigated to determine the reaction kinetics, transformation products, and changes in toxicity. The reaction between IDM and Fe(VI) followed first-order kinetics with respect to each reactant. The apparent second-order rate constants (k app ) decreased from 9.35 to 6.52 M -1  s -1 , as the pH of the solution increased from 7.0 to 10.0. The pH dependence of k app might be well explained by considering the species-specific rate constants of the reactions of IDM with Fe(VI). Detailed product studies using liquid chromatography-tandem mass spectrometry (LC-MS/MS) indicated that the oxidation products were primarily derived from the hydrolysis of amide linkages, the addition of hydroxyl groups, and electrophilic oxidation. The toxicity of the oxidation products was evaluated using the Microtox test, which indicated that transformation products exhibited less toxicity to the Vibrio fischeri bacteria. Quantitative structure-activity relationship (QSAR) analysis calculated by the ecological structure activity relationship (ECOSAR) revealed that all of the identified products exhibited lower acute and chronic toxicity than the parent pharmaceutical for fish, daphnid, and green algae. Furthermore, Fe(VI) was effective in the degradation IDM in water containing carbonate ions or fulvic acid (FA), and in lake water samples; however, higher Fe(VI) dosages would be required to completely remove IDM in lake water in contrast to deionized water.

Treatment of selected pharmaceuticals by ferrate(VI): performance, kinetic studies and identification of oxidation products.

PubMed

Zhou, Zhengwei; Jiang, Jia-Qian

2015-03-15

The performance of ferrate(VI) in treating sulfamethoxazole (SMX), diclofenac (DCF), carbamazepine (CBZ) and bezafibrate (BZF) in test solutions containing the four compounds was investigated. A series of jar-test experiments was performed on a bench-scale at pH 6-9 and at a ferrate(VI) dose of 1-5 mg Fe/L. The results suggested that ferrate(VI) can effectively remove SMX, DCF and CBZ from the test solutions, with greater than 80% removal under optimum conditions. However, the removal efficiency of BZF was very low, less than 25% under the studied conditions. Increasing the dose of ferrate(VI) improved the treatment performance, while the influence of solution pH on ferrate(VI) performance varied among the different target compounds. Ferrate(VI) demonstrated the highest reactivity with SMX at pH 8 and pH 9 (20 °C), with apparent second-order rate constants of 360±17 M(-1) s(-1) and 1.26±0.02 M(-1) s(-1), respectively. However, BZF showed the lowest removal by ferrate(VI) with the smallest rate constants (less than 0.5 M(-1) s(-1)) at pH 8 and pH 9. Furthermore, a number of oxidation products (OPs) of SMX, DCF and CBZ during ferrate(VI) oxidation were detected by liquid chromatography and mass spectrometry (LC-MS), and their degradation pathways were tentatively proposed. No OPs of BZF were detected during ferrate(VI) oxidation. Copyright © 2014 Elsevier B.V. All rights reserved.

Pre-steady-state kinetic studies of redox reactions catalysed by Bacillus subtilis ferredoxin-NADP(+) oxidoreductase with NADP(+)/NADPH and ferredoxin.

PubMed

Seo, Daisuke; Soeta, Takahiro; Sakurai, Hidehiro; Sétif, Pierre; Sakurai, Takeshi

2016-06-01

Ferredoxin-NADP(+) oxidoreductase ([EC1.18.1.2], FNR) from Bacillus subtilis (BsFNR) is a homodimeric flavoprotein sharing structural homology with bacterial NADPH-thioredoxin reductase. Pre-steady-state kinetics of the reactions of BsFNR with NADP(+), NADPH, NADPD (deuterated form) and B. subtilis ferredoxin (BsFd) using stopped-flow spectrophotometry were studied. Mixing BsFNR with NADP(+) and NADPH yielded two types of charge-transfer (CT) complexes, oxidized FNR (FNR(ox))-NADPH and reduced FNR (FNR(red))-NADP(+), both having CT absorption bands centered at approximately 600n m. After mixing BsFNR(ox) with about a 10-fold molar excess of NADPH (forward reaction), BsFNR was almost completely reduced at equilibrium. When BsFNR(red) was mixed with NADP(+), the amount of BsFNR(ox) increased with increasing NADP(+) concentration, but BsFNR(red) remained as the major species at equilibrium even with about 50-fold molar excess NADP(+). In both directions, the hydride-transfer was the rate-determining step, where the forward direction rate constant (~500 s(-1)) was much higher than the reverse one (<10 s(-1)). Mixing BsFd(red) with BsFNR(ox) induced rapid formation of a neutral semiquinone form. This process was almost completed within 1 ms. Subsequently the neutral semiquinone form was reduced to the hydroquinone form with an apparent rate constant of 50 to 70 s(-1) at 10°C, which increased as BsFd(red) increased from 40 to 120 μM. The reduction rate of BsFNR(ox) by BsFd(red) was markedly decreased by premixing BsFNR(ox) with BsFd(ox), indicating that the dissociation of BsFd(ox) from BsFNR(sq) is rate-limiting in the reaction. The characteristics of the BsFNR reactions with NADP(+)/NADPH were compared with those of other types of FNRs. Copyright © 2016 Elsevier B.V. All rights reserved.

Labview virtual instruments for calcium buffer calculations.

PubMed

Reitz, Frederick B; Pollack, Gerald H

2003-01-01

Labview VIs based upon the calculator programs of Fabiato and Fabiato (J. Physiol. Paris 75 (1979) 463) are presented. The VIs comprise the necessary computations for the accurate preparation of multiple-metal buffers, for the back-calculation of buffer composition given known free metal concentrations and stability constants used, for the determination of free concentrations from a given buffer composition, and for the determination of apparent stability constants from absolute constants. As implemented, the VIs can concurrently account for up to three divalent metals, two monovalent metals and four ligands thereof, and the modular design of the VIs facilitates further extension of their capacity. As Labview VIs are inherently graphical, these VIs may serve as useful templates for those wishing to adapt this software to other platforms.

Stable cycling in discrete-time genetic models.

PubMed

Hastings, A

1981-11-01

Examples of stable cycling are discussed for two-locus, two-allele, deterministic, discrete-time models with constant fitnesses. The cases that cycle were found by using numerical techniques to search for stable Hopf bifurcations. One consequence of the results is that apparent cases of directional selection may be due to stable cycling.

Thermodynamics of aragonite-strontianite solid solutions: Results from stoichiometric solubility at 25 and 76°C

USGS Publications Warehouse

Plummer, Niel; Busenberg, E.

1987-01-01

Neither equilibrium nor stoichiometric saturation is observed at 76°C during laboratory recrystallization of strontianite-aragonite solid solutions even after apparent 100 percent conversion to a narrow secondary composition and demonstration of a nearly constant composition system for periods of 300 hours.

[Grades evaluation of Scutellariae Radix slices based on quality constant].

PubMed

Deng, Zhe; Zhang, Jun; Jiao, Meng-Jiao; Zhong, Wen; Cui, Wen-Jin; Cheng, Jin-Tang; Chen, Sha; Wang, Yue-Sheng; Liu, An

2017-05-01

By measuring the morphological indexes and the marker components content of 22 batches of Scutellariae Radix slices as well as calculating the quality constant, this research was aimed to establish a new method of evaluating the specifications and grades of Scutellariae Radix slices. The quality constants of these samples were in the range of 0.04-0.49, which can be divided into several grades based on the real requirement. If they were divided into three grades, the quality constant was ≥0.39 for the first grade, <0.39 but ≥0.24 for the second grade, and <0.24 for the third grade. This work indicated that the quality constants characterizing both apparent parameters and intrinsic quality can be used as a comprehensive evaluation index to classify the grades of traditional Chinese medicine quantitatively, clearly and objectively. The research results in this paper would provide new ideas and references for evaluating the specifications and grades of traditional Chinese medicines. Copyright© by the Chinese Pharmaceutical Association.

Empirical Estimation of Local Dielectric Constants: Toward Atomistic Design of Collagen Mimetic Peptides

PubMed Central

Pike, Douglas H.; Nanda, Vikas

2017-01-01

One of the key challenges in modeling protein energetics is the treatment of solvent interactions. This is particularly important in the case of peptides, where much of the molecule is highly exposed to solvent due to its small size. In this study, we develop an empirical method for estimating the local dielectric constant based on an additive model of atomic polarizabilities. Calculated values match reported apparent dielectric constants for a series of Staphylococcus aureus nuclease mutants. Calculated constants are used to determine screening effects on Coulombic interactions and to determine solvation contributions based on a modified Generalized Born model. These terms are incorporated into the protein modeling platform protCAD, and benchmarked on a data set of collagen mimetic peptides for which experimentally determined stabilities are available. Computing local dielectric constants using atomistic protein models and the assumption of additive atomic polarizabilities is a rapid and potentially useful method for improving electrostatics and solvation calculations that can be applied in the computational design of peptides. PMID:25784456

Evaporation of liquid droplets on solid substrates. II. Periodic substrates with moving contact lines

NASA Astrophysics Data System (ADS)

Amini, Amirhossein; Homsy, G. M.

2017-04-01

Experiments on evaporating droplets on structured surfaces have shown that the contact line does not move with constant speed, but rather in a steplike "stick-slip" fashion. As a first step in understanding such behavior, we study the evaporation of a two-dimensional volatile liquid droplet on a nonplanar heated solid substrate with a moving contact line and fixed contact angle. The model for the flat case is adapted to include curved substrates, numerical solutions are achieved for various periodic and quasiperiodic substrate profiles, and the dynamics of the contact line and the apparent contact angle are studied. In contrast with our results for a flat substrate, for which the contact line recedes in a nearly constant speed, we observe that the contact line speed and position show significant time variation and that the contact line moves in an approximate steplike fashion on relatively steep substrates. For the simplest case of a periodic substrate, we find that the apparent contact angle is periodic in time. For doubly periodic substrates, we find that the apparent contact angle is periodic and that the problem exhibits a phase-locking behavior. For multimode quasiperiodic substrates, we find the contact line behavior to be temporally complex and not only limited to a stick-slip motion. In all cases, we find that the overall evaporation is increased relative to the flat substrate.

[Mathematic modeling and experimental validation of macrostate quality expression for multicomponent in Chinese materia medica].

PubMed

He, Fuyuan; Deng, Kaiwen; Shi, Jilian; Liu, Wenlong; Pi, Fengjuan

2011-11-01

To establish the unitive multicomponent quality system bridged macrostate mathematic model parameters of material quality and microstate component concentration for Chinese materia medica (CMM). According to law of biologic laws of thermodynamics, the state functions of macrostate qulity of the CMM were established. The validation test was carried out as modeling drug as alcohol extract of Radix Rhozome (AERR), their enthalpy of combustion was determined, and entropy and the capability of information by chromatographic fingerprint were assayed, and then the biologic apparent macrostate parameters were calculated. The biologic macrostate mathematic models, for the CMM quality controll, were established as parameters as the apparent equilibrium constant, biologic enthalpy, Gibbs free energy and biologic entropy etc. The total molarity for the 10 batchs of AERR were 0.153 4 mmol x g(-1) with 28.26% of RSD, with the average of apparent equilibrium constants, biologic enthalpy, Gibbs free energy and biologic entropy were 0.039 65, 8 005 J x mol(-1), -2.408 x 10(7) J x mol(-1) and - 8.078 x 10(4) J x K(-1) with RSD as 6.020%, 1.860%, 42.32% and 42.31%, respectively. The macrostate quality models for CMM can represent their intrinsic quality for multicomponent dynamic system such as the CMM, to manifest out as if the forest away from or tree near from to see it.

Prediction of radiation necrosis in a rodent model using magnetic resonance imaging apparent transverse relaxation (R_{2}^{*} )

NASA Astrophysics Data System (ADS)

Belliveau, Jean-Guy; Jensen, Michael D.; Stewart, James M. P.; Solovey, Igor; Klassen, L. Martyn; Bauman, Glenn S.; Menon, Ravi S.

2018-02-01

Background and purpose. Radiation necrosis remains an irreversible long-term side-effect following radiotherapy to the brain. The ability to predict areas that could ultimately develop into necrosis could lead to prevention and management of radiation necrosis. Materials and Methods. Fischer 344 rats were irradiated using two platforms (micro-CT irradiator and x-Rad 225 IGRT) with radiation up to 30 Gy for the micro-CT and 40 Gy for the xRAD-224 to half the brain. Animals were subsequently imaged using a 9.4 T MRI scanner every 2-4 weeks for up to 28 weeks using a 7-echo gradient echo sequence. The apparent transverse relaxation constant (R2* ) was calculated and retrospectively analyzed. Results. Animals irradiated with the low-dose rate micro-CT did not exhibit any symptoms or imaging changes associated with RN. Animals irradiated with the xRAD-225 exhibited imaging changes consistent with RN at week 24. Analysis of the R2* coefficient within the lesion and hippocampus shows the potential for detection of RN up to 10 weeks prior to morphological changes. Conclusions. The ability to predict areas of RN and increases of R2* within the hippocampus provides a method for long-term monitoring and prediction of RN.

Exposure to Fentanyl After Transdermal Patch Administration for Cancer Pain Management.

PubMed

Bista, Sudeep R; Haywood, Alison; Hardy, Janet; Norris, Ross; Hennig, Stefanie

2016-06-01

This study aimed to describe exposure after fentanyl transdermal patch administration in patients with advanced cancer to quantify variability around the exposure. Patients (n  =  56) with advanced cancer who received transdermal fentanyl (Durogesic®; median dose, 50 μg/h; range, 12-200 μg/h) provided venous blood samples (n  =  163) at various times (0.5-72 hours) during several patch application intervals. Plasma fentanyl concentration was determined (median, 0.9 μg/L; range, 0.04-9.7 μg/L) by high-performance liquid chromatography coupled to tandem mass spectrometry. Pharmacokinetic analysis was performed using nonlinear mixed-effects modeling with NONMEM. A 1-compartment distribution model with first-order absorption and elimination described fentanyl exposure after transdermal patch administration. Fentanyl apparent clearance (between-subject variability [BSV], %) was estimated at 122 L/h/70 kg and 38.5%, respectively. The absorption rate constant was 0.013 h(-1) . Between-occasion variability on apparent clearance was 22.0%, which was lower than BSV, suggesting predictable exposure within the same patient and justifying therapeutic drug monitoring. Except for weight-based dosing, no other patient characteristic could be identified to guide initial fentanyl dose selection in patients with advanced cancer. © 2015, The American College of Clinical Pharmacology.

The uptake of NO3-, NO2-, and NH4+ by intact wheat (Triticum aestivum) seedlings. I. Induction and kinetics of transport systems

NASA Technical Reports Server (NTRS)

Goyal, S. S.; Huffaker, R. C.

1986-01-01

The inducibility and kinetics of the NO3-, NO2-, and NH4+ transporters in roots of wheat seedlings (Triticum aestivum cv Yercora Rojo) were characterized using precise methods approaching constant analysis of the substrate solutions. A microcomputer-controlled automated high performance liquid chromatography system was used to determine the depletion of each N species (initially at 1 millimolar) from complete nutrient solutions. Uptake rate analyses were performed using computerized curve-fitting techniques. More precise estimates were obtained for the time required for the extent of the induction of each transporter. Up to 10 and 6 hours, respectively, were required to achieve apparent full induction of the NO3- and NO2- transporters. Evidence for substrate inducibility of the NH4+ transporters requiring 5 hours is presented. The transport of NO3- was mediated by a dual system (or dual phasic), whereas only single systems were found for transport of NO2- and NH4+. The Km values for NO3-, NO2-, and NH4+ were, respectively, 0.027, 0.054, and 0.05 millimolar. The Km for mechanism II of NO3- transport could not be defined in this study as it exhibited only apparent first order kinetics up to 1 millimolar.

Higher success rate with transcranial electrical stimulation of motor-evoked potentials using constant-voltage stimulation compared with constant-current stimulation in patients undergoing spinal surgery.

PubMed

Shigematsu, Hideki; Kawaguchi, Masahiko; Hayashi, Hironobu; Takatani, Tsunenori; Iwata, Eiichiro; Tanaka, Masato; Okuda, Akinori; Morimoto, Yasuhiko; Masuda, Keisuke; Tanaka, Yuu; Tanaka, Yasuhito

2017-10-01

During spine surgery, the spinal cord is electrophysiologically monitored via transcranial electrical stimulation of motor-evoked potentials (TES-MEPs) to prevent injury. Transcranial electrical stimulation of motor-evoked potential involves the use of either constant-current or constant-voltage stimulation; however, there are few comparative data available regarding their ability to adequately elicit compound motor action potentials. We hypothesized that the success rates of TES-MEP recordings would be similar between constant-current and constant-voltage stimulations in patients undergoing spine surgery. The objective of this study was to compare the success rates of TES-MEP recordings between constant-current and constant-voltage stimulation. This is a prospective, within-subject study. Data from 100 patients undergoing spinal surgery at the cervical, thoracic, or lumbar level were analyzed. The success rates of the TES-MEP recordings from each muscle were examined. Transcranial electrical stimulation with constant-current and constant-voltage stimulations at the C3 and C4 electrode positions (international "10-20" system) was applied to each patient. Compound muscle action potentials were bilaterally recorded from the abductor pollicis brevis (APB), deltoid (Del), abductor hallucis (AH), tibialis anterior (TA), gastrocnemius (GC), and quadriceps (Quad) muscles. The success rates of the TES-MEP recordings from the right Del, right APB, bilateral Quad, right TA, right GC, and bilateral AH muscles were significantly higher using constant-voltage stimulation than those using constant-current stimulation. The overall success rates with constant-voltage and constant-current stimulations were 86.3% and 68.8%, respectively (risk ratio 1.25 [95% confidence interval: 1.20-1.31]). The success rates of TES-MEP recordings were higher using constant-voltage stimulation compared with constant-current stimulation in patients undergoing spinal surgery. Copyright © 2017 Elsevier Inc. All rights reserved.

Elongational flow of polymer melts at constant strain rate, constant stress and constant force

NASA Astrophysics Data System (ADS)

Wagner, Manfred H.; Rolón-Garrido, Víctor H.

2013-04-01

Characterization of polymer melts in elongational flow is typically performed at constant elongational rate or rarely at constant tensile stress conditions. One of the disadvantages of these deformation modes is that they are hampered by the onset of "necking" instabilities according to the Considère criterion. Experiments at constant tensile force have been performed even more rarely, in spite of the fact that this deformation mode is free from necking instabilities and is of considerable industrial relevance as it is the correct analogue of steady fiber spinning. It is the objective of the present contribution to present for the first time a full experimental characterization of a long-chain branched polyethylene melt in elongational flow. Experiments were performed at constant elongation rate, constant tensile stress and constant tensile force by use of a Sentmanat Extensional Rheometer (SER) in combination with an Anton Paar MCR301 rotational rheometer. The accessible experimental window and experimental limitations are discussed. The experimental data are modelled by using the Wagner I model. Predictions of the steady-start elongational viscosity in constant strain rate and creep experiments are found to be identical, albeit only by extrapolation of the experimental data to Hencky strains of the order of 6. For constant stress experiments, a minimum in the strain rate and a corresponding maximum in the elongational viscosity is found at a Hencky strain of the order of 3, which, although larger than the steady-state value, follows roughly the general trend of the steady-state elongational viscosity. The constitutive analysis also reveals that constant tensile force experiments indicate a larger strain hardening potential than seen in constant elongation rate or constant tensile stress experiments. This may be indicative of the effect of necking under constant elongation rate or constant tensile stress conditions according to the Considère criterion.

Instanton rate constant calculations close to and above the crossover temperature.

PubMed

McConnell, Sean; Kästner, Johannes

2017-11-15

Canonical instanton theory is known to overestimate the rate constant close to a system-dependent crossover temperature and is inapplicable above that temperature. We compare the accuracy of the reaction rate constants calculated using recent semi-classical rate expressions to those from canonical instanton theory. We show that rate constants calculated purely from solving the stability matrix for the action in degrees of freedom orthogonal to the instanton path is not applicable at arbitrarily low temperatures and use two methods to overcome this. Furthermore, as a by-product of the developed methods, we derive a simple correction to canonical instanton theory that can alleviate this known overestimation of rate constants close to the crossover temperature. The combined methods accurately reproduce the rate constants of the canonical theory along the whole temperature range without the spurious overestimation near the crossover temperature. We calculate and compare rate constants on three different reactions: H in the Müller-Brown potential, methylhydroxycarbene → acetaldehyde and H 2  + OH → H + H 2 O. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Seasonal variability of light availability and utilization in the Sargasso Sea

NASA Technical Reports Server (NTRS)

Siegel, David A.; Michaels, Anthony F.; Sorensen, Jens C.; O'Brein, Margaret C.; Hammer, Melodie A.

1995-01-01

A 2 year time series of optical, biogeochemical, and physical parameters, taken near the island of Bermuda, is used to evaluate the sources of temporal variability in light avaliability and utilization in the Sargasso Sea. Integrated assessments of light availability are made by examining the depth of constant percent incident photosynthetically available radiation (% PAR) isolumes. To first order, changes in the depth %PAR isolumes were caused by physical processes: deep convection mixing in the winter which led to the spring bloom and concurrent shallowing of %PAR depths and the occurrence of anomalous thermohaline water masses during the summer and fall seasons. Spectral light availability variations are assessed using determinations of diffuse attenuation coefficient spectra which illustrates a significant seasonal cycle in colored detrital particulate and/or dissolved materials that is unrelated to changes in chlorophyll pigment concentrations. Temporal variations in the photosynthetic light utilization index Psi are used to assess vertically intergrated light utilization variations. Values of Psi are highly variable and show no apparent seasonal pattern which indicates that Psi is not simply a 'biogeochemical constant.' Determinations of in situ primary production rates and daily mean PAR fluxes are used to diagnose the relative role of light limitation in determining vertically integrated rates of primary production integral PP. The mean depth of the light-saturated zone (the vertical region where the daily mean PAR flux was greater than or equal to the saturation irradiance) is only approximately 40 m, although more than one half of interal PP occurred within this zone. Production model results illustrate that accurate predictions of integral PP are dependent upon rates of light-saturated production rather than upon indices of light limitation. It seems unlikely that significant improvements in simple primary production models will come from the partitioning of the Earth's seas into biogeochemical provinces.

Permanganate oxidation of diclofenac: The pH-dependent reaction kinetics and a ring-opening mechanism.

PubMed

Cheng, Hanyang; Song, Dean; Liu, Huijuan; Qu, Jiuhui

2015-10-01

In this work, the fate of diclofenac (DCF) during permanganate (Mn(VII)) oxidation was investigated at environmentally relevant pH conditions (from 5 to 9). The batch experiments showed that the kinetics of the Mn(VII)/DCF reaction follows a second-order rate law with an apparent rate constant of 1.57±0.02 M(-1) s(-1) at pH 7 and 20 °C. The half-value of DCF was calculated to be 37.5 min, when the concentration of Mn(VII) (0.4 mM) was 20-fold excess of DCF. The pH-dependence of the reaction kinetics was investigated, and the DCF reactivity with Mn(VII) was found to decrease with increasing pH. The second-order rate constants were then quantitatively described by incorporating the species distribution of DCF. A lower reactivity of the anionic DCF (DCF(-)) in comparison with its neutral counterpart (DCF(0)) was most likely attributable to the interaction between the ionized carboxylate group and amine nitrogen position, which can reduce the nucleophilicity of amine nitrogen by inductive and resonance effects. Moreover, a range of degradation products and the corresponding structures were proposed on the basis of the LC-Q-TOF-MS analysis. A detailed ring-opening reaction mechanism was proposed as follows: Mn(VII) acts as an electrophile to attack the amine moiety, leading to the formation of the primary intermediate products 2,6-dichloroaniline and 5-hydroxy-diclofenac, which can be further transformed. The further degradation proceeded through a multistep process including ring-opening, decarboxylation, hydroxylation, and cyclation reactions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Kinetic studies of Chromobacterium viscosum lipase in AOT water in oil microemulsions and gelatin microemulsion-based organogels.

PubMed

Jenta, T R; Batts, G; Rees, G D; Robinson, B H

1997-06-05

Kinetic studies have shown that octyl decanoate synthesis by Chromobacterium viscosum (CV) lipase in sodium bis-2-(ethylhexyl) sulfosuccinate (AOT) water in oil (w/o) microemulsions occurs via the nonsequential (ping-pong) bi bi mechanism. There was evidence of single substrate inhibition by decanoic acid at high concentrations. Initial rate data yielded estimates for acid and alcohol Michaelis constants of ca. 10(-1) mol dm(-3) and a maximum rate under saturation conditions of ca. 10(-3) mol dm(-3) s(-1) for a lipase concentration of 0.36 mg cm(-3). CV lipase immobilized in AOT microemulsion-based organogels (MBGs) was also found to catalyze the synthesis of octyl decanoate according to the ping-pong bi bi mechanism. Reaction rates were similar in the free and immobilized systems under comparable conditions. Initial rates at saturating (but noninhibiting) substrate concentrations were first order with respect to CV lipase concentration in both w/o microemulsions and the MBG/oil systems. Gradients yielded an apparent k(cat) = 4.4 x 10(-4) mol g(-1) s(-1) in the case of w/o microemulsions, and 6.1 x 10(-4) mol g(-1) s(-1) for CV lipase immobilized in the MBGs. A third system comprising w/o microemulsions containing substrates and gelatin at concentrations comparable to those employed in the MBG formulations, provided a useful link between the conventional liquid microemulsion medium and the solid organogels. The nongelation of these intermediate systems stems from the early inclusion of substrate during a modified preparative protocol. The presence of substrate appears to prevent the development of a percolated microstructure that is thought to be a prerequisite for MBG formation. FT-NMR was employed as a semicontinuous in situ assay procedure. The apparent activity expressed by CV lipase in compositionally equivalent liquid and solid phase gelatin-containing systems was similar. An apparent activation energy of 24 +/- 2 kJ mol(-1) was determined by (1)H-NMR for esterification in gelatin-containing w/o microemulsions. This value agrees with previous determinations for CV lipase-catalyzed synthesis of octyl decanoate in "conventional" w/o microemulsions and MBG/oil systems. The similarities in lipase behavior are consistent with the claim, based largely on structural measurements, that the physico-chemical properties of the lipase-containing w/o microemulsion are to a large extent preserved on transformation to the daughter organogel. The close agreement of apparrent activation energies suggests that substrate mass transfer is not rate determining in the three studied systems.

Simultaneous emission and transmission scanning in PET oncology: the effect on parameter estimation

NASA Astrophysics Data System (ADS)

Meikle, S. R.; Eberl, S.; Hooper, P. K.; Fulham, M. J.

1997-02-01

The authors investigated potential sources of bias due to simultaneous emission and transmission (SET) scanning and their effect on parameter estimation in dynamic positron emission tomography (PET) oncology studies. The sources of bias considered include: i) variation in transmission spillover (into the emission window) throughout the field of view, ii) increased scatter arising from rod sources, and iii) inaccurate deadtime correction. Net bias was calculated as a function of the emission count rate and used to predict distortion in [/sup 18/F]2-fluoro-2-deoxy-D-glucose (FDG) and [/sup 11/C]thymidine tissue curves simulating the normal liver and metastatic involvement of the liver. The effect on parameter estimates was assessed by spectral analysis and compartmental modeling. The various sources of bias approximately cancel during the early part of the study when count rate is maximal. Scatter dominates in the latter part of the study, causing apparently decreased tracer clearance which is more marked for thymidine than for FDG. The irreversible disposal rate constant, K/sub i/, was overestimated by <10% for FDG and >30% for thymidine. The authors conclude that SET has a potential role in dynamic FDG PET but is not suitable for /sup 11/C-labeled compounds.

Different Members of a Simple Three-Helix Bundle Protein Family Have Very Different Folding Rate Constants and Fold by Different Mechanisms

PubMed Central

Wensley, Beth G.; Gärtner, Martina; Choo, Wan Xian; Batey, Sarah; Clarke, Jane

2009-01-01

The 15th, 16th, and 17th repeats of chicken brain α-spectrin (R15, R16, and R17, respectively) are very similar in terms of structure and stability. However, R15 folds and unfolds 3 orders of magnitude faster than R16 and R17. This is unexpected. The rate-limiting transition state for R15 folding is investigated using protein engineering methods (Φ-value analysis) and compared with previously completed analyses of R16 and R17. Characterisation of many mutants suggests that all three proteins have similar complexity in the folding landscape. The early rate-limiting transition states of the three domains are similar in terms of overall structure, but there are significant differences in the patterns of Φ-values. R15 apparently folds via a nucleation–condensation mechanism, which involves concomitant folding and packing of the A- and C-helices, establishing the correct topology. R16 and R17 fold via a more framework-like mechanism, which may impede the search to find the correct packing of the helices, providing a possible explanation for the fast folding of R15. PMID:19445951

Trehalose and sorbitol alter the kinetic pattern of inactivation of glutamate dehydrogenase during drying in levitated microdroplets.

PubMed

Lorenzen, Elke; Lee, Geoffrey

2013-12-01

A single-droplet acoustic levitator was used to determine the drying rate and the kinetics of inactivation of glutamate dehydrogenase in the presence of added trehalose or sorbitol. The solution was also spray dried under the same process condition of drying gas temperature on a bench-top machine. Both trehalose and sorbitol delay the point of onset of enzyme inactivation which lies after the critical point of drying. Both carbohydrates also reduce the apparent rate constant of inactivation calculated during the subsequent inactivation phase. The carbohydrates stabilise, therefore, the enzyme during droplet drying and particle formation mainly during the falling rate drying period. There is no difference between the stabilising effects of the two carbohydrates when examined as levitated single droplets. This suggests the importance of water replacement as a stabilising mechanism in the levitated droplets/particles. On spray drying, the trehalose stabilises the enzyme better than does the sorbitol at a drying gas (outlet) temperature of 60°C. This suggests glass formation with the trehalose but not the sorbitol during the very rapid drying process of small-atomised droplets in the spray dryer. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association.

Propham mineralization in aqueous medium by anodic oxidation using boron-doped diamond anode: influence of experimental parameters on degradation kinetics and mineralization efficiency.

PubMed

Ozcan, Ali; Sahin, Yücel; Koparal, A Savaş; Oturan, Mehmet A

2008-06-01

This study aims the removal of a carbamate herbicide, propham, from aqueous solution by direct electrochemical advanced oxidation process using a boron-doped diamond (BDD) anode. This electrode produces large quantities of hydroxyl radicals from oxidation of water, which leads to the oxidative degradation of propham up to its total mineralization. Effect of operational parameters such as current, temperature, pH and supporting electrolyte on the degradation and mineralization rate was studied. The applied current and temperature exert a prominent effect on the total organic carbon (TOC) removal rate of the solutions. The mineralization of propham can be performed at any pH value between 3 and 11 without any loss in oxidation efficiency. The propham decay and its overall mineralization reaction follows a pseudo-first-order kinetics. The apparent rate constant value of propham oxidation was determined as 4.8 x 10(-4)s(-1) at 100 mA and 35 degrees C in the presence of 50mM Na(2)SO(4) in acidic media (pH: 3). A general mineralization sequence was proposed considering the identified oxidation intermediates.

Structural Insights into the TLA-3 Extended-Spectrum β-Lactamase and Its Inhibition by Avibactam and OP0595

PubMed Central

Jin, Wanchun; Yamaguchi, Yoshihiro; Kimura, Kouji; Kumar, Anupriya; Yamada, Mototsugu; Morinaka, Akihiro; Sakamaki, Yoshiaki; Yonezawa, Minoru; Kurosaki, Hiromasa; Arakawa, Yoshichika

2017-01-01

ABSTRACT The development of effective inhibitors that block extended-spectrum β-lactamases (ESBLs) and restore the action of β-lactams represents an effective strategy against ESBL-producing Enterobacteriaceae. We evaluated the inhibitory effects of the diazabicyclooctanes avibactam and OP0595 against TLA-3, an ESBL that we identified previously. Avibactam and OP0595 inhibited TLA-3 with apparent inhibitor constants (Ki app) of 1.71 ± 0.10 and 1.49 ± 0.05 μM, respectively, and could restore susceptibility to cephalosporins in the TLA-3-producing Escherichia coli strain. The value of the second-order acylation rate constant (k2/K, where k2 is the acylation rate constant and K is the equilibrium constant) of avibactam [(3.25 ± 0.03) × 103 M−1 · s−1] was closer to that of class C and D β-lactamases (k2/K, <104 M−1 · s−1) than that of class A β-lactamases (k2/K, >104 M−1 · s−1). In addition, we determined the structure of TLA-3 and that of TLA-3 complexed with avibactam or OP0595 at resolutions of 1.6, 1.6, and 2.0 Å, respectively. TLA-3 contains an inverted Ω loop and an extended loop between the β5 and β6 strands (insertion after Ser237), which appear only in PER-type class A β-lactamases. These structures might favor the accommodation of cephalosporins harboring bulky R1 side chains. TLA-3 presented a high catalytic efficiency (kcat/Km) against cephalosporins, including cephalothin, cefuroxime, and cefotaxime. Avibactam and OP0595 bound covalently to TLA-3 via the Ser70 residue and made contacts with residues Ser130, Thr235, and Ser237, which are conserved in ESBLs. Additionally, the sulfate group of the inhibitors formed polar contacts with amino acid residues in a positively charged pocket of TLA-3. Our findings provide a structural template for designing improved diazabicyclooctane-based inhibitors that are effective against ESBL-producing Enterobacteriaceae. PMID:28739781

Structural Insights into the TLA-3 Extended-Spectrum β-Lactamase and Its Inhibition by Avibactam and OP0595.

PubMed

Jin, Wanchun; Wachino, Jun-Ichi; Yamaguchi, Yoshihiro; Kimura, Kouji; Kumar, Anupriya; Yamada, Mototsugu; Morinaka, Akihiro; Sakamaki, Yoshiaki; Yonezawa, Minoru; Kurosaki, Hiromasa; Arakawa, Yoshichika

2017-10-01

The development of effective inhibitors that block extended-spectrum β-lactamases (ESBLs) and restore the action of β-lactams represents an effective strategy against ESBL-producing Enterobacteriaceae We evaluated the inhibitory effects of the diazabicyclooctanes avibactam and OP0595 against TLA-3, an ESBL that we identified previously. Avibactam and OP0595 inhibited TLA-3 with apparent inhibitor constants ( K i app ) of 1.71 ± 0.10 and 1.49 ± 0.05 μM, respectively, and could restore susceptibility to cephalosporins in the TLA-3-producing Escherichia coli strain. The value of the second-order acylation rate constant ( k 2 / K , where k 2 is the acylation rate constant and K is the equilibrium constant) of avibactam [(3.25 ± 0.03) × 10 3 M -1 · s -1 ] was closer to that of class C and D β-lactamases ( k 2 / K , <10 4 M -1 · s -1 ) than that of class A β-lactamases ( k 2 / K , >10 4 M -1 · s -1 ). In addition, we determined the structure of TLA-3 and that of TLA-3 complexed with avibactam or OP0595 at resolutions of 1.6, 1.6, and 2.0 Å, respectively. TLA-3 contains an inverted Ω loop and an extended loop between the β5 and β6 strands (insertion after Ser237), which appear only in PER-type class A β-lactamases. These structures might favor the accommodation of cephalosporins harboring bulky R1 side chains. TLA-3 presented a high catalytic efficiency ( k cat / K m ) against cephalosporins, including cephalothin, cefuroxime, and cefotaxime. Avibactam and OP0595 bound covalently to TLA-3 via the Ser70 residue and made contacts with residues Ser130, Thr235, and Ser237, which are conserved in ESBLs. Additionally, the sulfate group of the inhibitors formed polar contacts with amino acid residues in a positively charged pocket of TLA-3. Our findings provide a structural template for designing improved diazabicyclooctane-based inhibitors that are effective against ESBL-producing Enterobacteriaceae . Copyright © 2017 American Society for Microbiology.

O-acetylserine (thiol) lyase: an enigmatic enzyme of plant cysteine biosynthesis revisited in Arabidopsis thaliana.

PubMed

Wirtz, Markus; Droux, Michel; Hell, Rüdiger

2004-08-01

The synthesis of cysteine is positioned at a decisive stage of assimilatory sulphate reduction, marking the fixation of inorganic sulphide into a carbon skeleton. O-acetylserine (thiol) lyase (OAS-TL) catalyses the reaction of inorganic sulphide with O-acetylserine (OAS). Despite its prominent position in the pathway OAS-TL is generally regarded as a non-limiting enzyme without regulatory function, due to low substrate affinities and semi-constitutive expression patterns. To resolve this apparent contradiction, the kinetic properties of three OAS-TLs from Arabidopsis thaliana, localized in the cytosol (A), plastids (B), and mitochondria (C), were analysed. The recombinant expressed OAS-TLs were purified to apparent homogeneity without any fusion tag to maintain their native forms. The proteins displayed high specific activities of 550-900 micromol min(-1) mg(-1). Using an improved and highly sensitive assay method for cysteine determination, the apparent K(m)(sulphide) was 3-6 microM for OAS-TL A, B, and C and thus 10-100 times lower than previously reported for plant OAS-TLs. K(m)(OAS) was between 310 microM and 690 microM for OAS-TL isoform A, B, and C, whereas the apparent dissociation binding constant for OAS was much lower (K(d)<1 microM OAS). A HPLC method was developed for OAS quantification that revealed fast increases of the cellular OAS concentration in response to sulphate deprivation. The observed fluctuations of intracellular OAS concentrations, combined with the OAS dissociation constant and the catalytic properties of OAS-TL, support the model of a dynamic cysteine synthesis system with regulatory function as can be expected from the position of the reaction in the sulphur assimilation pathway.

Thermodynamic linkage between the binding of protons and inhibitors to HIV-1 protease.

PubMed Central

Trylska, J.; Antosiewicz, J.; Geller, M.; Hodge, C. N.; Klabe, R. M.; Head, M. S.; Gilson, M. K.

1999-01-01

The aspartyl dyad of free HIV-1 protease has apparent pK(a)s of approximately 3 and approximately 6, but recent NMR studies indicate that the aspartyl dyad is fixed in the doubly protonated form over a wide pH range when cyclic urea inhibitors are bound, and in the monoprotonated form when the inhibitor KNI-272 is bound. We present computations and measurements related to these changes in protonation and to the thermodynamic linkage between protonation and inhibition. The Poisson-Boltzmann model of electrostatics is used to compute the apparent pK(a)s of the aspartyl dyad in the free enzyme and in complexes with four different inhibitors. The calculations are done with two parameter sets. One assigns epsilon = 4 to the solute interior and uses a detailed model of ionization; the other uses epsilon = 20 for the solute interior and a simplified representation of ionization. For the free enzyme, both parameter sets agree well with previously measured apparent pK(a)s of approximately 3 and approximately 6. However, the calculations with an internal dielectric constant of 4 reproduce the large pKa shifts upon binding of inhibitors, but the calculations with an internal dielectric constant of 20 do not. This observation has implications for the accurate calculation of pK(a)s in complex protein environments. Because binding of a cyclic urea inhibitor shifts the pK(a)s of the aspartyl dyad, changing the pH is expected to change its apparent binding affinity. However, we find experimentally that the affinity is independent of pH from 5.5 to 7.0. Possible explanations for this discrepancy are discussed. PMID:10210196

Regulation of respiration in brain mitochondria and synaptosomes: restrictions of ADP diffusion in situ, roles of tubulin, and mitochondrial creatine kinase.

PubMed

Monge, Claire; Beraud, Nathalie; Kuznetsov, Andrey V; Rostovtseva, Tatiana; Sackett, Dan; Schlattner, Uwe; Vendelin, Marko; Saks, Valdur A

2008-11-01

The role of ubiquitous mitochondrial creatine kinase (uMtCK) reaction in regulation of mitochondrial respiration was studied in purified preparations of rat brain synaptosomes and mitochondria. In permeabilized synaptosomes, apparent Km for exogenous ADP, Km (ADP), in regulation of respiration in situ was rather high (110 +/- 11 microM) in comparison with isolated brain mitochondria (9 +/- 1 microM). This apparent Km for ADP observed in isolated mitochondria in vitro dramatically increased to 169 +/- 52 microM after their incubation with 1 muM of dimeric tubulin showing that in rat brain, particularly in synaptosomes, mitochondrial outer membrane permeability for ADP, and ATP may be restricted by tubulin binding to voltage dependent anion channel (VDAC). On the other hand, in synaptosomes apparent Km (ADP) decreased to 25 +/- 1 microM in the presence of 20 mM creatine. To fully understand this effect of creatine on kinetics of respiration regulation, complete kinetic analysis of uMtCK reaction in isolated brain mitochondria was carried out. This showed that oxidative phosphorylation specifically altered only the dissociation constants for MgATP, by decreasing that from ternary complex MtCK.Cr.MgATP (K (a)) from 0.13 +/- 0.02 to 0.018 +/- 0.007 mM and that from binary complex MtCK.MgATP (K (ia)) from 1.1 +/- 0.29 mM to 0.17 +/- 0.07 mM. Apparent decrease of dissociation constants for MgATP reflects effective cycling of ATP and ADP between uMtCK and adenine nucleotide translocase (ANT). These results emphasize important role and various pathophysiological implications of the phosphocreatine-creatine kinase system in energy transfer in brain cells, including synaptosomes.

Wetting Behavior of Calcium Ferrite Slags on Cristobalite Substrates

NASA Astrophysics Data System (ADS)

Yang, Mingrui; Lv, Xuewei; Wei, Ruirui; Xu, Jian; Bai, Chenguang

2018-03-01

Calcium ferrite (CF) is a significant intermediate adhesive phase in high-basicity sinters. The wettability between calcium ferrite (CF) and gangue plays an important role in the assimilation process. The wettability of CF-based slags, in which a constant amount (2 mass pct.) of Al2O3, MgO, SiO2, and TiO2 was added, on solid SiO2 (cristobalite) substrates at 1523 K (1250 °C) was investigated. The interfacial microstructure and spreading mechanisms were discussed for each sample. All the tested slag samples exhibited good wettability on the SiO2 substrate. The initial apparent contact angles were in the range of 20 to 50 deg, while the final apparent contact angles were 5 deg. The wetting process could be divided into three stages on the basis of the change in diameter, namely the "linear spreading" stage, "spreading rate reduction" stage, and "wetting equilibrium" stage. It was found that the CF-SiO2 wetting system exhibits dissolutive wetting and the dissolution of SiO2 into slag influences its spreading process. The spreading rate increases with a decrease in the ratio of viscosity to interfacial tension, which is a result of the addition of Al2O3, MgO, SiO2, and TiO2. After cooling, a deep corrosion pit was formed in the substrate and a diffusion layer was generated in front of the residual slag zone; further, some SiO2 and Fe2O3 solid solutions precipitated in the slag.

Wetting Behavior of Calcium Ferrite Slags on Cristobalite Substrates

NASA Astrophysics Data System (ADS)

Yang, Mingrui; Lv, Xuewei; Wei, Ruirui; Xu, Jian; Bai, Chenguang

2018-06-01

Calcium ferrite (CF) is a significant intermediate adhesive phase in high-basicity sinters. The wettability between calcium ferrite (CF) and gangue plays an important role in the assimilation process. The wettability of CF-based slags, in which a constant amount (2 mass pct.) of Al2O3, MgO, SiO2, and TiO2 was added, on solid SiO2 (cristobalite) substrates at 1523 K (1250 °C) was investigated. The interfacial microstructure and spreading mechanisms were discussed for each sample. All the tested slag samples exhibited good wettability on the SiO2 substrate. The initial apparent contact angles were in the range of 20 to 50 deg, while the final apparent contact angles were 5 deg. The wetting process could be divided into three stages on the basis of the change in diameter, namely the "linear spreading" stage, "spreading rate reduction" stage, and "wetting equilibrium" stage. It was found that the CF-SiO2 wetting system exhibits dissolutive wetting and the dissolution of SiO2 into slag influences its spreading process. The spreading rate increases with a decrease in the ratio of viscosity to interfacial tension, which is a result of the addition of Al2O3, MgO, SiO2, and TiO2. After cooling, a deep corrosion pit was formed in the substrate and a diffusion layer was generated in front of the residual slag zone; further, some SiO2 and Fe2O3 solid solutions precipitated in the slag.

The temperature dependence of the rate constant for the reaction of hydroxyl radicals with nitric acid

NASA Technical Reports Server (NTRS)

Kurylo, M. J.; Cornett, K. D.; Murphy, J. L.

1982-01-01

The rate constant for the reaction of hydroxyl radicals with nitric acid in the 225-443 K temperature range has been measured by means of the flash photolysis resonance fluorescence technique. Above 300 K, the rate constant levels off in a way that can only be explained by the occurrence of two reaction channels, of which one, operative at low temperatures, proceeds through the formation of an adduct intermediate. The implications of these rate constant values for stratospheric reaction constants is discussed.

Very high pressure liquid chromatography using core-shell particles: quantitative analysis of fast gradient separations without post-run times.

PubMed

Stankovich, Joseph J; Gritti, Fabrice; Stevenson, Paul G; Beaver, Lois A; Guiochon, Georges

2014-01-17

Five methods for controlling the mobile phase flow rate for gradient elution analyses using very high pressure liquid chromatography (VHPLC) were tested to determine thermal stability of the column during rapid gradient separations. To obtain rapid separations, instruments are operated at high flow rates and high inlet pressure leading to uneven thermal effects across columns and additional time needed to restore thermal equilibrium between successive analyses. The purpose of this study is to investigate means to minimize thermal instability and obtain reliable results by measuring the reproducibility of the results of six replicate gradient separations of a nine component RPLC standard mixture under various experimental conditions with no post-run times. Gradient separations under different conditions were performed: constant flow rates, two sets of constant pressure operation, programmed flow constant pressure operation, and conditions which theoretically should yield a constant net heat loss at the column's wall. The results show that using constant flow rates, programmed flow constant pressures, and constant heat loss at the column's wall all provide reproducible separations. However, performing separations using a high constant pressure with programmed flow reduces the analysis time by 16% compared to constant flow rate methods. For the constant flow rate, programmed flow constant pressure, and constant wall heat experiments no equilibration time (post-run time) was required to obtain highly reproducible data. Copyright © 2013 Elsevier B.V. All rights reserved.

The instantaneous apparent resistivity tensor: a visualization scheme for LOTEM electric field measurements

NASA Astrophysics Data System (ADS)

Caldwell, T. Grant; Bibby, Hugh M.

1998-12-01

Long-offset transient electromagnetic (LOTEM) data have traditionally been represented as early- and late-time apparent resistivities. Time-varying electric field data recorded in a LOTEM survey made with multiple sources can be represented by an `instantaneous apparent resistivity tensor'. Three independent, coordinate-invariant, time-varying apparent resistivities can be derived from this tensor. For dipolar sources, the invariants are also independent of source orientation. In a uniform-resistivity half-space, the invariant given by the square root of the tensor determinant remains almost constant with time, deviating from the half-space resistivity by a maximum of 6 per cent. For a layered half-space, a distance-time pseudo-section of the determinant apparent resistivity produces an image of the layering beneath the measurement profile. As time increases, the instantaneous apparent resistivity tensor approaches the direct current apparent resistivity tensor. An approximate time-to-depth conversion can be achieved by integrating the diffusion depth formula with time, using the determinant apparent resistivity at each instant to represent the resistivity of the conductive medium. Localized near-surface inhomogeneities produce shifts in the time-domain apparent resistivity sounding curves that preserve the gradient, analogous to static shifts seen in magnetotelluric soundings. Instantaneous apparent resistivity tensors calculated for 3-D resistivity models suggest that profiles of LOTEM measurements across a simple 3-D structure can be used to create an image that reproduces the main features of the subsurface resistivity. Where measurements are distributed over an area, maps of the tensor invariants can be made into a sequence of images, which provides a way of `time slicing' down through the target structure.

Non-thermal plasma-induced photocatalytic degradation of 4-chlorophenol in water.

PubMed

Hao, Xiao Long; Zhou, Ming Hua; Lei, Le Cheng

2007-03-22

TiO(2) photocatalyst (P-25) (50mgL(-1)) was tentatively introduced into pulsed high-voltage discharge process for non-thermal plasma-induced photocatalytic degradation of the representative mode organic pollutant parachlorophenol (4-CP), including other compounds phenol and methyl red in water. The experimental results showed that rate constant of 4-CP degradation, energy efficiency for 4-CP removal and TOC removal with TiO(2) were obviously increased. Pulsed high-voltage discharge process with TiO(2) had a promoted effect for the degradation of these pollutants under a broad range of liquid conductivity. Furthermore, the apparent formation rates of chemically active species (e.g., ozone and hydrogen peroxide) were increased, the hydrogen peroxide formation rate from 1.10x10(-6) to 1.50x10(-6)Ms(-1), the ozone formation rate from 1.99x10(-8) to 2.35x10(-8)Ms(-1), respectively. In addition, this process had no influence on the photocatalytic properties of TiO(2). The introduction of TiO(2) photocatalyst into pulsed discharge plasma process in the utilizing of ultraviolet radiation and electric field in pulsed discharge plasma process enhanced the yields of chemically active species, which were available for highly efficient removal and mineralization of organic pollutants.

Effect of surfactants on apparent oxygen consumption of photosystem I isolated from Arthrospira platensis.

PubMed

Yu, Daoyong; Huang, Guihong; Xu, Fengxi; Ge, Baosheng; Liu, Shuang; Xu, Hai; Huang, Fang

2014-11-01

Surfactants play a significant role in solubilization of photosystem I (PSI) in vitro. Triton X-100 (TX), n-Dodecyl-β-D-maltoside (DDM), and sodium dodecyl sulfate (SDS) were employed to solubilize PSI particles in MES buffer to compare the effect of surfactant and its dosage on the apparent oxygen consumption rate of PSI. Through a combined assessment of sucrose density gradient centrifugation, Native PAGE and 77 K fluorescence with the apparent oxygen consumption, the nature of the enhancement of the apparent oxygen consumption activity of PSI by surfactants has been analyzed. Aggregated PSI particles can be dispersed by surfactant molecules into micelles, and the apparent oxygen consumption rate is higher for surfactant-solubilized PSI than for integral PSI particles. For DDM, PSI particles are solubilized mostly as the integral trimeric form. For TX, PSI particles are solubilized as incomplete trimeric and some monomeric forms. For the much harsher surfactant, SDS, PSI particles are completely solubilized as monomeric and its subunit forms. The enhancement of the oxygen consumption rate cannot be explained only by the effects of surfactant on the equilibrium between monomeric and trimeric forms of solubililized PSI. Care must be taken when the electron transfer activity of PSI is evaluated by methods based on oxygen consumption because the apparent oxygen consumption rate is influenced by uncoupled chlorophyll (Chl) from PSI, i.e., the larger the amount of uncoupled Chl, the higher the rate of apparent oxygen consumption. 77 K fluorescence spectra can be used to ensure that there is no uncoupled Chl present in the system. In order to eliminate the effect of trace uncoupled Chl, an efficient physical quencher of (1)O2, such as 1 mM NaN3, may be added into the mixture.

Ionic channels and nerve membrane constituents. Tetrodotoxin-like interaction of saxitoxin with cholesterol monolayers.

PubMed

Villegas, R; Barnola, F V

1972-01-01

Saxitoxin (STX) and tetrodotoxin (TTX) have the same striking property of blocking the Na(+) channels in the axolemma. Experiments with nerve plasma membrane components of the squid Dosidicus gigas have shown that TTX interacts with cholesterol monolayers. Similar experiments were carried out with STX. The effect of STX on the surface pressure-area diagrams of lipid monolayers and on the fluorescence emission spectra of sonicated nerve membranes was studied. The results indicate a TTX-like interaction of STX with cholesterol monolayers. The expansion of the monolayers caused by 10(-6)M STX was 2.2 A(2)/cholesterol molecule at 25 degrees C. From surface pressure measurements at constant cholesterol area (39 A(2)/molecule) in media with various STX concentrations, it was calculated that the STX/cholesterol surface concentration ratio is 0.54. The apparent dissociation constant of the STX-cholesterol monolayer complex is 4.0 x 10(-7)M. The STX/cholesterol ratio and the apparent dissociation constant are similar to those determined for TTX. The presence of other lipids in the monolayers affects the STX-cholesterol association. The interactions of STX and TTX with cholesterol monolayers suggest (a) that cholesterol molecules may be part of the nerve membrane Na(+) channels, or (b) that the toxin receptor at the nerve membrane shares similar chemical features with the cholesterol monolayers.

Microplastic bases for constitutive characterization of aluminum alloys and their correlation to sheet formability

NASA Astrophysics Data System (ADS)

Diak, Bradley James

Forming limit predictions that incorporate crystal plasticity models still cannot adequately predict the deformation performance of polycrystalline materials. The reason for the limitation in predictive power is that the constitutive equations used to connect to the atomic scale assume an affine deformation which do not have a physical basis, but give general trends. This study was undertaken to better elucidate the microplastic process and how it manifests itself phenomenologically. In this endeavour, the strain rate sensitivity of the flow stress was identified as one parameter that greatly affects the forming limit. Hence, an attempt was made to properly define and measure the strain rate sensitivity according to the dictates of thermodynamics. The thermodynamics of systems can delineate the evolution of the state of a material if the state variables can be characterized and measured. Inevitably, these variables must be determined at constant structure. Using the theory of thermally activated flow, where the movement of dislocations past obstacles is the rate controlling step, the mechanical testing techniques have been designed to statistically assess the dynamic evolution of the microstructure by controlling the temperature, T, and strain rate, dotvarepsilon, and measuring the stress, sigma, mean slip distance, lambda, and mean slip velocity, dotlambda, to define sigma=f(lambda,dotlambda, T). The apparent activation volume, which characterizes the obstacle resistance of strain centres, is determined at constant structure by applying the strain rate change technique. Strain rate sensitivity data are compared to the Cottrell-Stokes relation, and the Haasen plot is used to separate the different contributions to the flow stress. Using these precise measurements at interrupted segments of strain, the evolution of a microstructure during plastic flow can be monitored. By this examination of different rate controlling obstacles, the microstructural parameters which correlate to formability were assessed. Detailed experimental evidence is given for different aluminum alloys containing mainly fast or slow diffusing solute species, transition precipitates, dispersed particles, and/or dislocation debris. These systems of Al-Fe, Al-Cr, Al-Cu, Al-Mg, and Al-Mg-Si, all displayed unique dislocation-defect interactions which could be elucidated by the current theory of thermally activated flow.

Mineral composition and rates of flow of effluent from the distal ileum of liquid-fed calves

PubMed Central

Smith, R. H.

1966-01-01

1. Liquid-fed calves (aged 1½-4 months) examined more than five weeks after inserting a re-entrant fistula into the distal ileum, of normal sodium and potassium status and without abnormal gut infection, showed mean emergence rates from the ileum for sodium, potassium and water of 2·3 m-mole/hr, 0·38 m-mole/hr and 21 g/hr respectively after 16 hr fasting. 2. Sodium and potassium emergence rates changed little when the residues from a milk or glucose-solution feed arrived at the distal ileum. When magnesium chloride was added to a glucose-solution feed an increase sometimes occurred but only in association with decreased small-intestine transit time. 3. Widely differing sodium and potassium intakes had no appreciable direct effect on their emergence rates. Continued feeding of a diet deficient in either ion, however, altered the calf's metabolism and led to appropriate changes in the sodium/potassium ratio of ileal effluent. These changes were not simulated by injecting adrenal cortex hormones. The ratio also decreased when ileal effluent was allowed to discharge for several weeks without being returned to the colon. It was abnormally high in samples obtained less than five weeks after inserting cannulae. 4. An increase in sodium and potassium emergence rates, which often occurred spontaneously at about 3 months of age, appeared to be due to infection and was usually prevented by giving aureomycin orally. 5. Water emergence rate reflected changes in the emergence rates of osmotically effective constituents and isotonicity was maintained. In effluent after fasting, the cations involved were mainly sodium and potassium, and [Na] + [K] was approximately constant (mean 132 m-mole/l.). In effluent following feeds of milk or glucose, magnesium chloride solution, [Na] + [K] was depressed and [Na] + [K] + 1·5 [Mg] was approximately constant (mean 139 m-mole/l.). Magnesium behaved as it were mainly ionic. Calcium had no apparent osmotic effect and was probably insoluble. 6. Bicarbonate was the major anion in ileal effluent after a milk feed with smaller amounts of chloride, phosphate and some other unknown anion(s). PMID:5919555

Direct dynamics simulations of the unimolecular dissociation of dioxetane: Probing the non-RRKM dynamics

NASA Astrophysics Data System (ADS)

Malpathak, Shreyas; Ma, Xinyou; Hase, William L.

2018-04-01

In a previous UB3LYP/6-31G* direct dynamics simulation, non-Rice-Ramsperger-Kassel-Marcus (RRKM) unimolecular dynamics was found for vibrationally excited 1,2-dioxetane (DO); [R. Sun et al., J. Chem. Phys. 137, 044305 (2012)]. In the work reported here, these dynamics are studied in more detail using the same direct dynamics method. Vibrational modes of DO were divided into 4 groups, based on their characteristic motions, and each group excited with the same energy. To compare with the dynamics of these groups, an additional group of trajectories comprising a microcanonical ensemble was also simulated. The results of these simulations are consistent with the previous study. The dissociation probability, N(t)/N(0), for these excitation groups were all different. Groups A, B, and C, without initial excitation in the O-O stretch reaction coordinate, had a time lag to of 0.25-1.0 ps for the first dissociation to occur. Somewhat surprisingly, the C-H stretch Group A and out-of-plane motion Group C excitations had exponential dissociation probabilities after to, with a rate constant ˜2 times smaller than the anharmonic RRKM value. Groups B and D, with excitation of the H-C-H bend and wag, and ring bend and stretch modes, respectively, had bi-exponential dissociation probabilities. For Group D, with excitation localized in the reaction coordinate, the initial rate constant is ˜7 times larger than the anharmonic RRKM value, substantial apparent non-RRKM dynamics. N(t)/N(0) for the random excitation trajectories was non-exponential, indicating intrinsic non-RRKM dynamics. For the trajectory integration time of 13.5 ps, 9% of these trajectories did not dissociate in comparison to the RRKM prediction of 0.3%. Classical power spectra for these trajectories indicate they have regular intramolecular dynamics. The N(t)/N(0) for the excitation groups are well described by a two-state coupled phase space model. From the intercept of N(t)/N(0) with random excitation, the anharmonic correction to the RRKM rate constant is approximately a factor of 1.5.

Kinetics of Ca2+ binding to parvalbumin in bovine chromaffin cells: implications for [Ca2+] transients of neuronal dendrites

PubMed Central

Lee, Suk-Ho; Schwaller, Beat; Neher, Erwin

2000-01-01

The effect of parvalbumin (PV) on [Ca2+] transients was investigated by perfusing adrenal chromaffin cells with fura-2 and fluorescein isothiocyanate (FITC)-labelled PV. As PV diffused into cells, the decay of [Ca2+] transients was transformed from monophasic into biphasic. The proportion of the initial fast decay phase increased in parallel with the fluorescence intensity of FITC, indicating that PV is responsible for the initial fast decay phase.The relationship between the fast decay phase and the [Ca2+] level was investigated using depolarizing trains of stimuli. Within a train the relative amplitude of the fast decay phase was inversely dependent on the [Ca2+] level preceding a given stimulus.Based on these observations, we estimated the Ca2+ binding ratio of PV (κP), the apparent dissociation constant of PV for Ca2+ (Kdc,app), and the unbinding rate constant of Ca2+ from PV (kc-) in the cytosol of chromaffin cells. Assuming free [Mg2+] to be 0.14 mm, we obtained values of 51.4 ± 2.0 nm (n = 3) and 0.95 ± 0.026 s−1 (n = 3), for Kdc,app and kc-, respectively.With the parameters obtained in the perfusion study, we simulated [Ca2+] transients, using two different Ca2+ extrusion rates (γ) – 20 and 300 s−1– which represent typical values for chromaffin cells and neuronal dendrites, respectively. The simulation indicated that Ca2+ is pumped out before it is equilibrated with PV, when γ is comparable to the equilibration rates between PV and Ca2+, resulting in the fast decay phase of a biexponential [Ca2+] transient.From these results we conclude that Ca2+ buffers with slow kinetics, such as PV, may cause biexponential decays in [Ca2+] transients, thereby complicating the analysis of endogenous Ca2+ binding ratios (κS) based on time constants. Nevertheless, estimates of κS based on Ca2+ increments provide reasonable estimates for Ca2+ binding ratios before equilibration with PV. PMID:10835044

L-tryptophan-induced electron transport across supported lipid bilayers: an alkyl-chain tilt-angle, and bilayer-symmetry dependence.

PubMed

Sarangi, Nirod Kumar; Patnaik, Archita

2012-12-21

Molecular orientation-dependent electron transport across supported 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) lipid bilayers (SLBs) on semiconducting indium tin oxide (ITO) is reported with an aim towards potential nanobiotechnological applications. A bifunctional strategy is adopted to form symmetric and asymmetric bilayers of DPPC that interact with L-tryptophan, and are analyzed by surface manometry and atomic force microscopy. Polarization-dependent real-time Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS) analysis of these SLBs reveals electrostatic, hydrogen-bonding, and cation-π interactions between the polar head groups of the lipid and the indole side chains. Consequently, a molecular tilt arises from the effective interface dipole, facilitating electron transport across the ITO-anchored SLBs in the presence of an internal Fe(CN)(6)(4-/3-) redox probe. The incorporation of tryptophan enhances the voltammetric features of the SLBs. The estimated electron-transfer rate constants for symmetric and asymmetric bilayers (k(s) = 2.0×10(-2) and 2.8×10(-2) s(-1)) across the two-dimensional (2D) ordered DPPC/tryptophan SLBs are higher compared to pure DPPC SLBs (k(s) = 3.2×10(-3) and 3.9×10(-3) s(-1)). In addition, they are molecular tilt-dependent, as it is the case with the standard apparent rate constants k(app)(0), estimated from electrochemical impedance spectroscopy and bipotentiostatic experiments with a Pt ultramicroelectrode. Lower magnitudes of k(s) and k(app)(0) imply that electrochemical reactions across the ITO-SLB electrodes are kinetically limited and consequently governed by electron tunneling across the SLBs. Standard theoretical rate constants (k(th)(0)) accrued upon electron tunneling comply with the potential-independent electron-tunneling coefficient β = 0.15 Å(-1). Insulator-semiconductor transitions moving from a liquid-expanded to a condensed 2D-phase state of the SLBs are noted, adding a new dimension to their transport behavior. These results highlight the role of tryptophan in expediting electron transfer across lipid bilayer membranes in a cellular environment and can provide potential clues towards patterned lipid nanocomposites and devices. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rate Constants and Mechanisms of Protein–Ligand Binding

PubMed Central

Pang, Xiaodong; Zhou, Huan-Xiang

2017-01-01

Whereas protein–ligand binding affinities have long-established prominence, binding rate constants and binding mechanisms have gained increasing attention in recent years. Both new computational methods and new experimental techniques have been developed to characterize the latter properties. It is now realized that binding mechanisms, like binding rate constants, can and should be quantitatively determined. In this review, we summarize studies and synthesize ideas on several topics in the hope of providing a coherent picture of and physical insight into binding kinetics. The topics include microscopic formulation of the kinetic problem and its reduction to simple rate equations; computation of binding rate constants; quantitative determination of binding mechanisms; and elucidation of physical factors that control binding rate constants and mechanisms. PMID:28375732

Effect of temperature on Brettanomyces bruxellensis: metabolic and kinetic aspects.

PubMed

Brandam, Cédric; Castro-Martínez, Claudia; Délia, Marie-Line; Ramón-Portugal, Felipe; Strehaiano, Pierre

2008-01-01

The effect of temperatures ranging from 15 to 35 degrees C on a culture of Brettanomyces bruxellensis was investigated in regards to thermodynamics, metabolism, and kinetics. In this temperature range, we observed an increase in growth and production rates. The growth behavior was well represented using the Arrhenius model, and an apparent activation energy of 16.61 kcal/mol was estimated. A stuck fermentation was observed at 35 degrees C as represented by high cell death. The carbon balance established that temperature had no effect on repartition of the glucose consumption between biomass and products. Hence, the same biomass concentration was obtained for all temperatures, except at 35 degrees C. Moreover, using logistic and Luedeking-Piret models, we demonstrated that production rates of ethanol and acetic acid were partially growth associated. Parameters associated with growth (alpha eth and alpha aa) remained constant with changing temperature, whereas, parameters associated with the population (beta eth and beta aa) varied. Optimal values were obtained at 32 degrees C for ethanol and at 25 degrees C for acetic acid.

Kinetics of Methylmercury Production Revisited

DOE PAGES

Olsen, Todd A.; Muller, Katherine A.; Painter, Scott L.; ...

2018-01-27

Laboratory measurements of the biologically mediated methylation of mercury (Hg) to the neurotoxin monomethylmercury (MMHg) often exhibit kinetics that are inconsistent with first-order kinetic models. Using time-resolved measurements of filter passing Hg and MMHg during methylation/demethylation assays, a multisite kinetic sorption model, and reanalyses of previous assays, we show in this paper that competing kinetic sorption reactions can lead to time-varying availability and apparent non-first-order kinetics in Hg methylation and MMHg demethylation. The new model employing a multisite kinetic sorption model for Hg and MMHg can describe the range of behaviors for time-resolved methylation/demethylation data reported in the literature includingmore » those that exhibit non-first-order kinetics. Additionally, we show that neglecting competing sorption processes can confound analyses of methylation/demethylation assays, resulting in rate constant estimates that are systematically biased low. Finally, simulations of MMHg production and transport in a hypothetical periphyton biofilm bed illustrate the implications of our new model and demonstrate that methylmercury production may be significantly different than projected by single-rate first-order models.« less

Variable-speed controller provides flexibility to electrical submersible pumps

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

Butlin, D.

1986-06-09

The performance of an electric submersible pump (ESP) is dramatically modified by a variable speed controller (VSC). Variable frequency power directly controls pump speed and thus the hydraulic performance of the pump. Even though the ESP is the primary form of artificial lift for high volume, deep oil wells (particularly where gas is unavailable), the biggest disadvantage has been the pump's inflexibility when run at a constant speed, i.e., the unit is limited to a fixed head output at each rate. The VSC has rapidly gained acceptance as a valuable ESP accessory to alleviate this restriction. By allowing the pumpmore » speed to be varied, the rate and head, or both, can be adjusted with no modification of the downhole unit. There are now over 700 VSCs running with ESPs on every continent of the world. Pumping flexibility was the main purpose of applying the VSC to the ESP, but several other benefits have become apparent. Of particular interest are those that can extend downhole equipment life, e.g., soft start, automatically controlled speed, line-transient suppression, and elimination of surface chokes.« less

Novel carbapenem derivative SF2103A: studies on the mode of beta-lactamase inactivation.

PubMed Central

Yamaguchi, A; Hirata, T; Sawai, T

1984-01-01

A novel carbapenem, SF2103A, is a strong inhibitor of various types of beta-lactamase. Equimolar concentrations of SF2103A completely inactivated the cephalosporinases of Proteus vulgaris and Citrobacter freundii and type Ib and type II penicillinases mediated by R plasmids in a progressive manner. The inactivation of the two penicillinases and P. vulgaris cephalosporinase was apparently irreversible; however, when the inactivated enzymes were separated from excess SF2103A by gel filtration, they showed very slow reactivation. The hydrolysis of SF2103A by these three beta-lactamases was below the limit of detection. It is concluded that SF2103A acts as a tight-binding competitive inhibitor for the penicillinases and P. vulgaris cephalosporinase. In contrast, the inactivation of C. freundii cephalosporinase by SF2103A was evidently reversible. The rate constant of reactivation of the enzyme was compatible with the turnover rate of the enzyme in the steady state of SF2103A hydrolysis. Thus, SF2103A simply acts as a poor substrate for C. freundii cephalosporinase. PMID:6372682

Oxidation of diclofenac by potassium ferrate (VI): reaction kinetics and toxicity evaluation.

PubMed

Wang, Yingling; Liu, Haijin; Liu, Guoguang; Xie, Youhai; Gao, Shuyan

2015-02-15

The reaction kinetics and toxicity of diclofenac (DCF) oxidation by ferrate (VI) under simulated water disinfection conditions were investigated. Experimental results indicated that the reaction between DCF and Fe(VI) followed first-order kinetics with respect to each reactant. Furthermore, the effects of pH and temperature on DCF oxidation by Fe(VI) were elucidated using a systematic examination. The apparent second-order rate constants (kapp) increased significantly from 2.54 to 11.6M(-1)s(-1), as the pH of the solution decreased from 11.0 to 7.0, and the acid-base equilibriums of Fe(VI) and DCF were proposed to explain the pH dependence of kapp. The acute toxicity of DCF solution during Fe(VI) oxidation was evaluated using a Microtox bioassay. Overall, the DCF degradation process resulted in a rapid increase of the inhibition rate of luminescent bacteria. These toxicity tests suggest that the formation of enhanced toxic intermediates during the Fe(VI) disinfection process may pose potential health risk to consumers. Copyright © 2014 Elsevier B.V. All rights reserved.

Rate Constant and Temperature Dependence for the Reaction of Hydroxyl Radicals with 2-Flouropropane (FC-281ea) and Comparison with an Estimated Rate Constant

NASA Technical Reports Server (NTRS)

DeMore, W.; Wilson, E., Jr.

1998-01-01

Relative rate experiments were used to measure the rate constant and temperature dependence of the reaction of OH radicals with 2-fluoropropane (HFC-281ea), using ethane, propane, ethyl chloride as reference standards.

Examination of worldwide hardwood lumber production, trade, and apparent consumption: 1995-2013

Treesearch

William G. Luppold; Matthew S. Bumgardner

2015-01-01

Worldwide hardwood lumber production fluctuated between 1995 and 2013 and changed considerably with respect to regional market shares. Similarly, worldwide hardwood lumber imports and exports have been constantly changing. Understanding these changes is important because collectively, they define the hardwood lumber consumption of a region or country. In 1995, North...

Observational analysis of the well-correlated diffuse bands: 6196 and 6614 Å

NASA Astrophysics Data System (ADS)

Krełowski, J.; Galazutdinov, G. A.; Bondar, A.; Beletsky, Y.

2016-08-01

We confirm, using spectra from seven observatories, that the diffuse bands 6196 and 6614 are very tightly correlated. However, their strength ratio is not constant as well as profile shapes. Apparently, the two interstellar features do not react in unison to the varying physical conditions of different interstellar clouds.

Measurements of dispersion forces between colloidal latex particles with the atomic force microscope and comparison with Lifshitz theory

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

Elzbieciak-Wodka, Magdalena; Ruiz-Cabello, F. Javier Montes; Trefalt, Gregor

2014-03-14

Interaction forces between carboxylate colloidal latex particles of about 2 μm in diameter immersed in aqueous solutions of monovalent salts were measured with the colloidal probe technique, which is based on the atomic force microscope. We have systematically varied the ionic strength, the type of salt, and also the surface charge densities of the particles through changes in the solution pH. Based on these measurements, we have accurately measured the dispersion forces acting between the particles and estimated the apparent Hamaker constant to be (2.0 ± 0.5) × 10{sup −21} J at a separation distance of about 10 nm. Thismore » value is basically independent of the salt concentration and the type of salt. Good agreement with Lifshitz theory is found when roughness effects are taken into account. The combination of retardation and roughness effects reduces the value of the apparent Hamaker constant and its ionic strength dependence with respect to the case of ideally smooth surfaces.« less

Modification of the Selectivity Properties of Tubular Ceramic Membranes after Alkaline Treatment

PubMed Central

Dutournié, Patrick; Limousy, Lionel; Anquetil, Jérôme

2017-01-01

This work focuses on the selectivity modification of ceramic membranes after a mild alkaline treatment. Filtration of pure salt-water solutions was carried out with commercial titania membranes before and after the treatment. After treatment, the rejection of NaF significantly decreased, while the rejection of NaCl and NaBr increased. Additionally, NaI and Na2SO4 remained close to zero. Pore size and electrical charge being almost unchanged, only significant modifications in the dielectric effects can explain this modification of selectivity. Therefore, the surface chemistry and the interaction (nature and magnitude) with the solvent and with the species present in the solution appear to be modified by the alkaline treatment. This trend is also illustrated by discussing the electric and the dielectric properties that were numerically identified before and after treatment. The alkaline treatment significantly decreased the apparent dielectric constant of NaCl-water solution in the pore, highlighting the rejection of sodium chloride. Contrariwise, the modification of the surface chemistry increased the apparent dielectric constant of NaF-water solution by promoting fluoride transmission. PMID:29160802

Modification of the Selectivity Properties of Tubular Ceramic Membranes after Alkaline Treatment.

PubMed

Dutournié, Patrick; Limousy, Lionel; Anquetil, Jérôme; Déon, Sébastien

2017-11-21

This work focuses on the selectivity modification of ceramic membranes after a mild alkaline treatment. Filtration of pure salt-water solutions was carried out with commercial titania membranes before and after the treatment. After treatment, the rejection of NaF significantly decreased, while the rejection of NaCl and NaBr increased. Additionally, NaI and Na₂SO₄ remained close to zero. Pore size and electrical charge being almost unchanged, only significant modifications in the dielectric effects can explain this modification of selectivity. Therefore, the surface chemistry and the interaction (nature and magnitude) with the solvent and with the species present in the solution appear to be modified by the alkaline treatment. This trend is also illustrated by discussing the electric and the dielectric properties that were numerically identified before and after treatment. The alkaline treatment significantly decreased the apparent dielectric constant of NaCl-water solution in the pore, highlighting the rejection of sodium chloride. Contrariwise, the modification of the surface chemistry increased the apparent dielectric constant of NaF-water solution by promoting fluoride transmission.

Rapid estimation of glucosinolate thermal degradation rate constants in leaves of Chinese kale and broccoli (Brassica oleracea) in two seasons.

PubMed

Hennig, Kristin; Verkerk, Ruud; Bonnema, Guusje; Dekker, Matthijs

2012-08-15

Kinetic modeling was used as a tool to quantitatively estimate glucosinolate thermal degradation rate constants. Literature shows that thermal degradation rates differ in different vegetables. Well-characterized plant material, leaves of broccoli and Chinese kale plants grown in two seasons, was used in the study. It was shown that a first-order reaction is appropriate to model glucosinolate degradation independent from the season. No difference in degradation rate constants of structurally identical glucosinolates was found between broccoli and Chinese kale leaves when grown in the same season. However, glucosinolate degradation rate constants were highly affected by the season (20-80% increase in spring compared to autumn). These results suggest that differences in glucosinolate degradation rate constants can be due to variation in environmental as well as genetic factors. Furthermore, a methodology to estimate rate constants rapidly is provided to enable the analysis of high sample numbers for future studies.

Methane steam reforming rates over Pt, Rh and Ni(111) accounting for H tunneling and for metal lattice vibrations

NASA Astrophysics Data System (ADS)

German, Ernst D.; Sheintuch, Moshe

2017-02-01

Microkinetic models of methane steam reforming (MSR) over bare platinum and rhodium (111) surfaces are analyzed in present work using calculated rate constants. The individual rate constants are classified into three different sets: (i) rate constants of adsorption and desorption steps of CH4, H2O, CO and of H2; (ii) rate constants of dissociation and formation of A-H bonds (A = C, O, and H), and (iii) rate constants of dissociation and formation of C-O bond. The rate constants of sets (i) and (iii) are calculated using transition state theory and published thermochemical data. The rate constants of H-dissociation reactions (set (ii)) are calculated in terms of a previously-developed approach that accounts for thermal metal lattice vibrations and for H tunneling through a potential barrier of height which depends on distance of AH from a surface. Pre-exponential factors of several group (ii) steps were calculated to be usually lower than the traditional kBT/h due to tunneling effect. Surface composition and overall MSR rates over platinum and rhodium surfaces are compared with those over nickel surface showing that operating conditions strongly affect on the activity order of the catalysts.

Anti-Arrhenius cleavage of covalent bonds in bottlebrush macromolecules on substrate

PubMed Central

Lebedeva, Natalia V.; Nese, Alper; Sun, Frank C.; Matyjaszewski, Krzysztof; Sheiko, Sergei S.

2012-01-01

Spontaneous degradation of bottlebrush macromolecules on aqueous substrates was monitored by atomic force microscopy. Scission of C─C covalent bonds in the brush backbone occurred due to steric repulsion between the adsorbed side chains, which generated bond tension on the order of several nano-Newtons. Unlike conventional chemical reactions, the rate of bond scission was shown to decrease with temperature. This apparent anti-Arrhenius behavior was caused by a decrease in the surface energy of the underlying substrate upon heating, which results in a corresponding decrease of bond tension in the adsorbed macromolecules. Even though the tension dropped minimally from 2.16 to 1.89 nN, this was sufficient to overpower the increase in the thermal energy (kBT) in the Arrhenius equation. The rate constant of the bond-scission reaction was measured as a function of temperature and surface energy. Fitting the experimental data by a perturbed Morse potential V = V0(1 - e-βx)2 - fx, we determined the depth and width of the potential to be V0 = 141 ± 19 kJ/mol and β-1 = 0.18 ± 0.03 Å, respectively. Whereas the V0 value is in reasonable agreement with the activation energy Ea = 80–220 kJ/mol of mechanical and thermal degradation of organic polymers, it is significantly lower than the dissociation energy of a C─C bond De = 350 kJ/mol. Moreover, the force constant Kx = 2β2V0 = 1.45 ± 0.36 kN/m of a strained bottlebrush along its backbone is markedly larger than the force constant of a C─C bond Kl = 0.44 kN/m, which is attributed to additional stiffness due to deformation of the side chains. PMID:22645366

The rate of mental health service use in New Zealand as analysed by ethnicity.

PubMed

Tapsell, Rees; Hallett, Charlene; Mellsop, Graham

2018-06-01

To compare by ethnicity the rates of apparent new referrals and admissions to mental health services for selected major diagnostic groupings. Using a Ministry of Health database covering all referrals and admissions to New Zealand's Mental Health services in 2014 and who had not been patients in the preceding six years, population adjusted rates of presentation were calculated and compared across the two major New Zealand ethnic groupings. Population corrected rates of apparently new cases of schizophrenia are more than twice as common in Māori as in non-Māori. Major depression is also significantly more common in Māori. That same trend was not evident for bipolar patients. These ethnically associated apparent differences in the rates of schizophrenia and depression need both confirmation and explanation.

Prediction of Chain Propagation Rate Constants of Polymerization Reactions in Aqueous NIPAM/BIS and VCL/BIS Systems.

PubMed

Kröger, Leif C; Kopp, Wassja A; Leonhard, Kai

2017-04-06

Microgels have a wide range of possible applications and are therefore studied with increasing interest. Nonetheless, the microgel synthesis process and some of the resulting properties of the microgels, such as the cross-linker distribution within the microgels, are not yet fully understood. An in-depth understanding of the synthesis process is crucial for designing tailored microgels with desired properties. In this work, rate constants and reaction enthalpies of chain propagation reactions in aqueous N-isopropylacrylamide/N,N'-methylenebisacrylamide and aqueous N-vinylcaprolactam/N,N'-methylenebisacrylamide systems are calculated to identify the possible sources of an inhomogeneous cross-linker distribution in the resulting microgels. Gas-phase reaction rate constants are calculated from B2PLYPD3/aug-cc-pVTZ energies and B3LYPD3/tzvp geometries and frequencies. Then, solvation effects based on COSMO-RS are incorporated into the rate constants to obtain the desired liquid-phase reaction rate constants. The rate constants agree with experiments within a factor of 2-10, and the reaction enthalpies deviate less than 5 kJ/mol. Further, the effect of rate constants on the microgel growth process is analyzed, and it is shown that differences in the magnitude of the reaction rate constants are a source of an inhomogeneous cross-linker distribution within the resulting microgel.

StimuFrac Compressibility as a Function of CO2 Molar Fraction

DOE Data Explorer

Carlos A. Fernandez

2016-04-29

Compressibility values were obtained in a range of pressures at 250degC by employing a fixed volume view cell completely filled with PAA aqueous solution and injecting CO2 at constant flow rate (0.3mL/min). Pressure increase as a function of supercritical CO2 (scCO2) mass fraction in the mixture was monitored. The plot shows the apparent compressibility of Stimufrac as a function of scCO2 mass fraction obtained in a pressure range between 2100-7000 psi at 250degC. At small mass fractions of scCO2 the compressibility increases probably due to the dissolution/reaction of CO2 in aqueous PAA and reaches a maximum at mCO2/mH2O = 0.06. Then, compressibility decreases showing a linear relationship with scCO2 mass fraction due to the continuous increase in density of the binary fluid associated to the pressure increase.

Relaxation and anomalous T- and H-dependence of the μ coefficient in (K,Ba)BiO3 superconductors

NASA Astrophysics Data System (ADS)

Klein, T.; Harneit, W.; Joumard, I.; Marcus, J.; Escribe-Filippini, C.; Feinberg, D.

1998-04-01

Ac shielding and classical dc relaxation experiments have been used to study the flux creep phenomena in the cubic (K,Ba)BiO3 superconductor (Tc ~ 30 K). The relaxation rate is found to be constant (S ~ 1.5%) at low temperature and magnetic field and increases sharply as the vortex-glass transition line is approached. This behavior can be attributed to an anomalous decrease of the μ exponent (U(J) = U0(J0/J)μ) close to Tg(H). In this regime, the temperature dependence of the apparent critical current J is then directly related to μ(T) as J(T) = J0/[kT/U0·ln (1/ωτ)]μ(T). A similar analysis can be made on the J(B) data recently published by Abulafia et al. (Phys. Rev. Lett., 77 (1996) 1597) on YBaCuO single crystals.

An asteroid breakup 160 Myr ago as the probable source of the K/T impactor.

PubMed

Bottke, William F; Vokrouhlický, David; Nesvorný, David

2007-09-06

The terrestrial and lunar cratering rate is often assumed to have been nearly constant over the past 3 Gyr. Different lines of evidence, however, suggest that the impact flux from kilometre-sized bodies increased by at least a factor of two over the long-term average during the past approximately 100 Myr. Here we argue that this apparent surge was triggered by the catastrophic disruption of the parent body of the asteroid Baptistina, which we infer was a approximately 170-km-diameter body (carbonaceous-chondrite-like) that broke up 160(-20)+30Myr ago in the inner main asteroid belt. Fragments produced by the collision were slowly delivered by dynamical processes to orbits where they could strike the terrestrial planets. We find that this asteroid shower is the most likely source (>90 per cent probability) of the Chicxulub impactor that produced the Cretaceous/Tertiary (K/T) mass extinction event 65 Myr ago.

Modelling of photodegradation in solar cell modules of substrate and superstrate design made with ethylene-vinyl acetate as pottant material

NASA Technical Reports Server (NTRS)

Somersall, A. C.; Guillet, J. E.

1983-01-01

A computer model was developed which can generate realistic concentration versus time profiles of the chemical species formed during photooxidation of hydrocarbon polymers using as input data a set of elementary reactions with corresponding rate constants and initial conditions. The results of computer simulation have been shown to be consistent with the general experimental observations of the photooxidation of polyethylene exposed to sunlight at ambient temperatures. The useful lifetime (5% oxidation) of the unstabilized polyethylene is predicted to vary from a few months in hot weather (100 F) to almost two years in cool weather (45 F) with an apparent net activation energy of 10 kcal/mol. Modelling studies of alternate mechanisms for stabilization of clear, amorphous, linear polyethylene suggest that the optimum stabilizer would be a molecularly dispensed additive in very low concentration which can trap peroxy radicals and also decompose hydroperoxides.

Thermodynamic and kinetic studies of As2O3 toxicological effects on human insulin in generation diabetes mellitus

NASA Astrophysics Data System (ADS)

Mohsennia, Mohsen; Motaharinejad, Atieh; Rafiee-Pour, Hossain-Ali; Torabbeigi, Marzieh

2017-12-01

The interaction of arsenic trioxide with human insulin was investigated by circular dichroism (CD), cyclic voltammetry and electrophoresis techniques. The interfacial behavior of insulin in presence of As2O3 onto the Ag electrode surface was studied at 310 K in phosphate buffer solution (PBS). According to Far-UV CD spectroscopy results, As2O3 caused to decrease in structural compactness and variety of alpha helix into beta structures. Near-UV CD indicated that As2O3 dissociates disulfide linkage in insulin structure. The kinetic parameters, including charge-transfer coefficient and apparent heterogeneous electron transfer rate constant were also determined. The thermodynamic parameters of insulin denaturation in presence of arsenic trioxide were calculated and reported. The obtained results indicated strong adsorption of insulin in presence of arsenic trioxide onto the Ag surface via chemisorptions.

On the politics and practice of Muslim fertility: comparative evidence from West Africa.

PubMed

Johnson-Hanks, Jennifer

2006-03-01

Recent popular works have represented Muslim fertility as dangerously high, both a cause and consequence of religious fundamentalism. This article uses comparative, statistical methods to show that this representation is empirically wrong, at least in West Africa. Although religion strongly inflects reproductive practice, its effects are not constant across different communities. In West African countries with Muslim majorities, Muslim fertility is lower than that of their non-Muslim conationals; in countries where Muslims are in the minority, their apparently higher reproductive rates converge to those of the majority when levels of education and urban residence are taken into account. A similar pattern holds for infant mortality. By contrast, in all seven countries, Muslim women are more likely to report that their most recent child was wanted. The article concludes with a discussion of the relationship between autonomy and fertility desires.

Rheological behavior, emulsifying properties and structural characterization of phosphorylated fish gelatin.

PubMed

Huang, Tao; Tu, Zong-Cai; Shangguan, Xinchen; Wang, Hui; Sha, Xiaomei; Bansal, Nidhi

2018-04-25

Rheological, microstructural and emulsifying properties of fish gelatin phosphorylated using sodium trimetaphosphate (STMP) were studied. Phosphorylation was carried out at 50 °C for 0, 0.5, 1 or 2 h. Rheological behaviors indicated that phosphorylation decreased gelation rate constant (k gel ) and apparent viscosity of gelatin solutions. Phosphorylation time was inversely proportional to tan δ; gelling and melting points of fish gelatin gels; however gel properties could be improved by short time of phosphorylation. Scanning electron microscopy and atomic force microscopy revealed that longer time of phosphorylation resulted in looser gel network with more aggregation. Longer phosphorylation time could stabilize fish gelatin emulsions, and endowed emulsions with smaller particle size and lower coefficient viscosity, but higher ζ-potential values. These results suggested that phosphorylation could be applied to obtain fish gelatin with varying functional properties suitable for numerous industrial applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Temperature influence on the malonic acid decomposition in the Belousov-Zhabotinsky reaction

NASA Astrophysics Data System (ADS)

Blagojević, S. M.; Anić, S. R.; Čupić, Ž. D.; Pejić, N. D.; Kolar-Anić, Lj. Z.

2009-09-01

The kinetic investigations of the malonic acid decomposition (8.00 × 10-3 mol dm-3 ≤ [CH2(COOH)2]0 ≤ 4.30 × 10-2 mol dm-3) in the Belousov-Zhabotinsky (BZ) system in the presence of bromate, bromide, sulfuric acid and cerium sulfate, were performed in the isothermal closed well stirred reactor at different temperatures (25.0°C ≤ T ≤ 45.0°C). The formal kinetics of the overall BZ reaction, and particularly kinetics in characteristic periods of BZ reaction, based on the analyses of the bromide oscillograms, was accomplished. The evolution as well as the rate constants and the apparent activation energies of the reactions, which exist in the preoscillatory and oscillatory periods, are also successfully calculated by numerical simulations. Simulations are based on the model including the Br2O species.

Telomere length dynamics differ in foetal and early post-natal human leukocytes in a longitudinal study.

PubMed

Holmes, Denise K; Bellantuono, Ilaria; Walkinshaw, Steve A; Alfirevic, Zarko; Johnston, Tracey A; Subhedar, Nimish V; Chittick, Rachel; Swindell, Richard; Wynn, Robert F

2009-06-01

Haemopoietic stem cells (HSC) undergo a process of self renewal to constantly maintain blood cell turnover. However, it has become apparent that adult HSC lose their self-renewal ability with age. Telomere shortening in peripheral blood leukocytes has been seen to occur with age and it has been associated with loss of HSC proliferative capacity and cellular ageing. In contrast foetal HSC are known to have greater proliferative capacity than post-natal stem cells. However it is unknown whether they undergo a similar process of telomere shortening. In this study we show a more accentuated rate of telomere loss in leukocytes from pre term infants compared to human foetuses of comparable age followed longitudinally for 8-12 weeks in a longitudinal study. Our results point to a difference in HSC behaviour between foetal and early postnatal life which is independent of age but may be influenced by events at birth itself.

Intracellular pressure is a motive force for cell motion in Amoeba proteus.

PubMed

Yanai, M; Kenyon, C M; Butler, J P; Macklem, P T; Kelly, S M

1996-01-01

The cortical filament layer of free-living amoebae contains concentrated actomyosin, suggesting that it can contract and produce an internal hydrostatic pressure. We report here on direct and dynamic intracellular pressure (P(ic)) measurements in Amoeba proteus made using the servo-null technique. In resting apolar A. proteus, P(ic) increased while the cells remained immobile and at apparently constant volume. P(ic) then decreased approximately coincident with pseudopod formation. There was a positive correlation between P(ic) at the onset of movement and the rate of pseudopod formation. These results are the first direct evidence that hydrostatic pressure may be a motive force for cell motion. We postulate that contractile elements in the amoeba's cortical layer contract and increase P(ic) and that this P(ic) is utilized to overcome the viscous flow resistance of the intracellular contents during pseudopod formation.

The equilibrium assumption is valid for the kinetic treatment of most time-dependent protein-modification reactions.

PubMed Central

Brocklehurst, K

1979-01-01

To facilitate mechanistic interpretation of the kinetics of time-dependent inhibition of enzymes and of similar protein modification reactions, it is important to know when the equilibrium assumption may be applied to the model: formula: (see text). The conventional criterion of quasi-equilibrium, k + 2 less than k-1, is not always easy to assess, particularly when k + 2 cannot be separately determined. It is demonstrated that the condition k + 2 less than k-1 is necessarily true, however, when the value of the apparent second-order rate constant for the modification reaction is much smaller than the value of k + 1. Since k + 1 is commonly at least 10(7)M-1.S-1 for substrates, it is probable that the equilibrium assumption may be properly applied to most irreversible inhibitions and modification reactions. PMID:518556

Persistence and biodegradation of spilled residual fuel oil on an estuarine beach.

PubMed

Pierce, R H; Cundell, A M; Traxler, R W

1975-05-01

The enrichment of hydrocarbon-degrading bacteria and the persistence of petroleum hydrocarbons on an estuarine beach after a spill of residual fuel oil on 11 April 1973 in Upper Narragansett Bay, R.I. was investigated. A rapid enrichment occurred during days 4 to 16 after the oil spill and a significant population of hydrocarbon-degrading bacteria was maintained in the beach sand for at least a year. The concentration of petroleum hydrocarbons in the mid-tide area declined rapidly during the bacterial enrichment period, remained fairly constant throughout the summer, and then declined to a low concentration after 1 year. An increased concentration of branched and cyclic aliphatic hydrocarbons in the low-tide sediment 128 days after the spill suggested a migration of hydrocarbons during the summer. Hydrocarbon biodegradation was apparent during the winter months at a rate of less than 1 mug of hydrocarbon per g of dry sediment per day.

Microcomputer-Based Programs for Pharmacokinetic Simulations.

ERIC Educational Resources Information Center

Li, Ronald C.; And Others

1995-01-01

Microcomputer software that simulates drug-concentration time profiles based on user-assigned pharmacokinetic parameters such as central volume of distribution, elimination rate constant, absorption rate constant, dosing regimens, and compartmental transfer rate constants is described. The software is recommended for use in undergraduate…

Removal of ammoniacal nitrogen from landfill leachate by irrigation onto vegetated treatment planes.

PubMed

Tyrrel, S F; Leeds-Harrison, P B; Harrison, K S

2002-01-01

Leachate is a contaminated liquor resulting from the disposal of solid and liquid wastes at landfill sites that must be treated before discharge. Vegetated leachate treatment planes have been used at landfill sites in the UK but have received little scientific attention. This paper describes studies of model leachate treatment planes with a focus on the removal of ammoniacal nitrogen (NH3-N). Small-scale and field-scale experimental treatment planes were constructed. filled with clay loam soil and vegetated with grass (Agrostis stolonifera). Landfill leachate was applied at hydraulic loading rates ranging from 17-217l/m2/d. An exponential relationship was used to characterise the pattern of NH3-N removal. No relationship was observed between the hydraulic loading rate and the NH3-N removal rate constants (R2 = 0.0039). The daily specific NH3-N mass removal rate was found to be linearly related to the NH3-N concentration at the start of that day of treatment (R2 = 0.35). Possible causes of variation in the rate of NH3-N removal between experiments are discussed. A simple inorganic nitrogen balance indicated that the mass of N-H3-N and NO2-N removed was not accounted for by NO3-N production. Explanations for this apparent nitrogen deficit are discussed.

Effect of Infection by Hypomyces solani f. sp. Cucurbitac on Apparent Free Space, Cell Membrane Permeability, and Respiration of Squash Hypocotyls 1

PubMed Central

Hancock, Joseph G.

1968-01-01

Initial symptoms and increases in respiration, apparent free space, and rate of leakage of amino acids occurred concomitantly in squash (Cucurbita maxima Dcne) hypocotyls infected by Hypomyces solani f. sp. cucurbitae Snyd. and Hans. Young, rapidly expanding lesions had greater respiratory rates and apparent free space than comparable tissues from healthy plants. Hypocotyl tissues above (1-45 mm) lesions possessed greater endogenous respiratory rates (2-3 times) and lower respiratory quotients than similar tissues from healthy plants. But no differences were found in membrane permeability to nonelectrolytes and water and in apparent free space between cells above lesions and healthy hypocotyls. Host cells contiguous to fungal hyphae at lesion margins were completely permeable to solutes and failed to accumulate neutral red or exhibit cyclosis. Images PMID:16656953

Dust Effects on Nucleation Kinetics and Nanoparticle Product Size Distributions: Illustrative Case Study of a Prototype Ir(0)n Transition-Metal Nanoparticle Formation System.

PubMed

Özkar, Saim; Finke, Richard G

2017-07-05

The question is addressed if dust is kinetically important in the nucleation and growth of Ir(0) n nanoparticles formed from [Bu 4 N] 5 Na 3 (1,5-COD)Ir I ·P 2 W 15 Nb 3 O 62 (hereafter [(COD)Ir·POM] 8- ), reduced by H 2 in propylene carbonate solvent. Following a concise review of the (often-neglected) literature addressing dust in nucleation phenomena dating back to the late 1800s, the nucleation and growth kinetics of the [(COD)Ir·POM] 8- precatalyst system are examined for the effects of 0.2 μm microfiltration of the solvent and precatalyst solution, of rinsing the glassware with that microfiltered solvent, of silanizing the glass reaction vessel, for the addition of <0.2 μm γ-Al 2 O 3 (inorganic) dust, for the addition of flame-made carbon-based (organic) dust, and as a function of the starting, microfiltered [(COD)Ir·POM 8- ] concentration. Efforts to detect dust and its removal by dynamic light scattering and by optical microscopy are also reported. The results yield a list of eight important conclusions, the four most noteworthy of which are (i) that the nucleation apparent rate "constant" k 1obs(bimol) is shown to be slowed by a factor of ∼5 to ∼7.6, depending on the precise experiment and its conditions, just by the filtration of the precatalyst solution using a 0.20 μm filter and rinsing the glassware surface with 0.20 μm filtered propylene carbonate solvent; (ii) that simply employing a 0.20 μm filtration step narrows the size distribution of the resulting Ir(0) n nanoparticles by a factor of 2.4 from ±19 to ±8%, a remarkable result; (iii) that the narrower size distribution can be accounted for by the slowed nucleation rate constant, k 1obs(bimol) , and by the unchanged autocatalytic growth rate constant, k 2obs(bimol) , that is, by the increased ratio of k 2obs(bimol) /k 1obs(bimol) that further separates nucleation from growth in time for filtered vs unfiltered solutions; and (iv) that five lines of evidence indicate that the filterable component of the solution, which has nucleation rate-enhancing and size-dispersion broadening effects, is dust.

Mechanisms of Enhanced Catalysis in Enzyme-DNA Nanostructures Revealed through Molecular Simulations and Experimental Analysis.

PubMed

Gao, Yingning; Roberts, Christopher C; Toop, Aaron; Chang, Chia-En A; Wheeldon, Ian

2016-08-03

Understanding and controlling the molecular interactions between enzyme substrates and DNA nanostructures has important implications in the advancement of enzyme-DNA technologies as solutions in biocatalysis. Such hybrid nanostructures can be used to create enzyme systems with enhanced catalysis by controlling the local chemical and physical environments and the spatial organization of enzymes. Here we have used molecular simulations with corresponding experiments to describe a mechanism of enhanced catalysis due to locally increased substrate concentrations. With a series of DNA nanostructures conjugated to horseradish peroxidase, we show that binding interactions between substrates and the DNA structures can increase local substrate concentrations. Increased local substrate concentrations in HRP(DNA) nanostructures resulted in 2.9- and 2.4-fold decreases in the apparent Michaelis constants of tetramethylbenzidine and 4-aminophenol, substrates of HRP with tunable binding interactions to DNA nanostructures with dissociation constants in the micromolar range. Molecular simulations and kinetic analysis also revealed that increased local substrate concentrations enhanced the rates of substrate association. Identification of the mechanism of increased local concentration of substrates in close proximity to enzymes and their active sites adds to our understanding of nanostructured biocatalysis from which we can develop guidelines for enhancing catalysis in rationally designed systems. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exploration of two-enzyme coupled catalysis system using scanning electrochemical microscopy.

PubMed

Wu, Zeng-Qiang; Jia, Wen-Zhi; Wang, Kang; Xu, Jing-Juan; Chen, Hong-Yuan; Xia, Xing-Hua

2012-12-18

In biological metabolism, a given metabolic process usually occurs via a group of enzymes working together in sequential pathways. To explore the metabolism mechanism requires the understanding of the multienzyme coupled catalysis systems. In this paper, an approach has been proposed to study the kinetics of a two-enzyme coupled reaction using SECM combining numerical simulations. Acetylcholine esterase and choline oxidase are immobilized on cysteamine self-assembled monolayers on tip and substrate gold electrodes of SECM via electrostatic interactions, respectively. The reaction kinetics of this two-enzyme coupled system upon various separation distance precisely regulated by SECM are measured. An overall apparent Michaelis-Menten constant of this enzyme cascade is thus measured as 2.97 mM at an optimal tip-substrate gap distance of 18 μm. Then, a kinetic model of this enzyme cascade is established for evaluating the kinetic parameters of individual enzyme by using the finite element method. The simulated results demonstrate the choline oxidase catalytic reaction is the rate determining step of this enzyme cascade. The Michaelis-Menten constant of acetylcholine esterase is evaluated as 1.8 mM. This study offers a promising approach to exploring mechanism of other two-enzyme coupled reactions in biological system and would promote the development of biosensors and enzyme-based logic systems.

Direct electrochemistry of glucose oxidase and glucose biosensing on a hydroxyl fullerenes modified glassy carbon electrode.

PubMed

Gao, Yun-Fei; Yang, Tian; Yang, Xiao-Lu; Zhang, Yu-Shuai; Xiao, Bao-Lin; Hong, Jun; Sheibani, Nader; Ghourchian, Hedayatollah; Hong, Tao; Moosavi-Movahedi, Ali Akbar

2014-10-15

Direct electrochemistry of glucose oxidase (GOD) was achieved when GOD-hydroxyl fullerenes (HFs) nano-complex was immobilized on a glassy carbon (GC) electrode and protected with a chitosan (Chit) membrane. The ultraviolet-visible absorption spectrometry (UV-vis), transmission electron microscopy (TEM), and circular dichroism spectropolarimeter (CD) methods were utilized for additional characterization of the GOD, GOD-HFs and Chit/GOD-HFs. Chit/HFs may preserve the secondary structure and catalytic properties of GOD. The cyclic voltammograms (CVs) of the modified GC electrode showed a pair of well-defined quasi-reversible redox peaks with the formal potential (E°') of 353 ± 2 mV versus Ag/AgCl at a scan rate of 0.05 V/s. The heterogeneous electron transfer constant (ks) was calculated to be 2.7 ± 0.2s(-1). The modified electrode response to glucose was linear in the concentrations ranging from 0.05 to 1.0mM, with a detection limit of 5 ± 1 μM. The apparent Michaelis-Menten constant (Km(app)) was 694 ± 8 μM. Thus, the modified electrode could be applied as a third generation biosensor for glucose with high sensitivity, selectivity and low detection limit. Copyright © 2014 Elsevier B.V. All rights reserved.

Direct electron transfer of glucose oxidase and biosensing for glucose based on PDDA-capped gold nanoparticle modified graphene/multi-walled carbon nanotubes electrode.

PubMed

Yu, Yanyan; Chen, Zuanguang; He, Sijing; Zhang, Beibei; Li, Xinchun; Yao, Meicun

2014-02-15

In this work, poly (diallyldimethylammonium chloride) (PDDA)-capped gold nanoparticles (AuNPs) functionalized graphene (G)/multi-walled carbon nanotubes (MWCNTs) nanocomposites were fabricated. Based on the electrostatic attraction, the G/MWCNTs hybrid material can be decorated with AuNPs uniformly and densely. The new hierarchical nanostructure can provide a larger surface area and a more favorable microenvironment for electron transfer. The AuNPs/G/MWCNTs nanocomposite was used as a novel immobilization platform for glucose oxidase (GOD). Direct electron transfer (DET) was achieved between GOD and the electrode. Field emission scanning electron microscopy (FESEM), UV-vis spectroscopy and cyclic voltammetry (CV) were used to characterize the electrochemical biosensor. The glucose biosensor fabricated based on GOD electrode modified with AuNPs/G/MWCNTs demonstrated satisfactory analytical performance with high sensitivity (29.72mAM(-1)cm(-2)) and low limit of detection (4.8 µM). The heterogeneous electron transfer rate constant (ΚS) and the apparent Michaelis-Menten constant (Km) of GOD were calculated to be 11.18s(-1) and 2.09 mM, respectively. With satisfactory selectivity, reproducibility, and stability, the nanostructure we proposed offered an alternative for electrode fabricating and glucose biosensing. © 2013 Elsevier B.V. All rights reserved.

Molecular clock or erratic evolution? A tale of two genes.

PubMed Central

Ayala, F J; Barrio, E; Kwiatowski, J

1996-01-01

We have investigated the evolution of glycerol-3-phosphate dehydrogenase (Gpdh). The rate of amino acid replacements is 1 x 10(-10)/site/year when Drosophila species are compared. The rate is 2.7 times greater when Drosophila and Chymomyza species are compared; and about 5 times greater when any of those species are compared with the medfly Ceratitis capitata. This rate of 5 x 10(-10)/site/year is also the rate observed in comparisons between mammals, or between different animal phyla, or between the three multicellular kingdoms. We have also studied the evolution of Cu,Zn superoxide dismutase (Sod). The rate of amino acid replacements is about 17 x 10(-10)/site/year when comparisons are made between dipterans or between mammals, but only 5 x 10(-10) when animal phyla are compared, and only 3 x 10(-10) when the multicellular kingdoms are compared. The apparent decrease by about a factor of 5 in the rate of SOD evolution as the divergence between species increases can be consistent with the molecular clock hypothesis by assuming the covarion hypothesis (namely, that the number of amino acids that can change is constant, but the set of such amino acids changes from time to time and from lineage to lineage). However, we know of no model consistent with the molecular clock hypothesis that would account for the increase in the rate of GPDH evolution as the divergence between species increases. Images Fig. 2 Fig. 5 PMID:8876205

Affinity capillary electrophoresis and density functional theory study of noncovalent interactions of cyclic peptide [Gly6 ]-antamanide with small cations.

PubMed

Pangavhane, Sachin; Böhm, Stanislav; Makrlík, Emanuel; Ruzza, Paolo; Kašička, Václav

2017-08-01

ACE and density functional theory were employed to study the noncovalent interactions of cyclic decapeptide glycine-6-antamanide ([Gly 6 ]AA), synthetic derivative of native antamanide (AA) peptide from the deadly poisonous fungus Amanita phalloides, with small cations (Li + , Rb + , Cs + , NH 4 + , and Ca 2+ ) in methanol. The strength of these interactions was quantified by the apparent stability constants of the appropriate complexes determined by ACE. The stability constants were calculated using the nonlinear regression analysis of the dependence of the effective electrophoretic mobility of [Gly 6 ]AA on the concentration of the above ions in the BGE (methanolic solution of 20 mM chloroacetic acid, 10 mM Tris, pH MeOH 7.8, containing 0-70 mM concentrations of the above ions added in the form of chlorides). Prior to stability constant calculation, the effective mobilities measured at actual temperature inside the capillary and at variable ionic strength of the BGEs were corrected to the values corresponding to the reference temperature of 25°C and to the constant ionic strength of 10 mM. From the above ions, Rb + and Cs + cations interacted weakly with [Gly 6 ]AA but no interactions of [Gly 6 ]AA with univalent Li + and NH 4 + ions and divalent Ca 2+ ion were observed. The apparent stability constants of [Gly 6 ]AA-Rb + and [Gly 6 ]AA-Cs + complexes were found to be equal to 13 ± 4 and 22 ± 3 L/mol, respectively. The structural characteristics of these complexes, such as position of the Rb + and Cs + ions in the cavity of the [Gly 6 ]AA molecule and the interatomic distances within these complexes, were obtained by the density functional theory calculations. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evidence for two distinct intracellular pools of inorganic sulfate in Penicillium notatum

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

Hunter, D.R.; Segel, I.H.

1985-06-01

A strain of Penicillium notatum unable to metabolize inorganic sulfate can accumulate sulfate internally to an apparent equilibrium concentration 10/sup 5/ times greater than that remaining in the medium. The apparent K/sub eq/ is near constant at all initial external sulfate concentrations below that which would eventually exceed the internal capacity of the cells. Under equilibrium conditions of zero net flux, external /sup 35/SO/sub 4//sup 2 -/ exchanges with internal, unlabeled SO/sub 4//sup 2 -/ at a rate consistent with the kinetic constants with the sulfate transport system. Efflux experiments demonstrated that sulfate occupies two distinct intracellular pools. Pool 1more » is characterized by the rapid release of /sup 35/SO/sub 4//sup 2 -/ when the suspension of preloaded cells is adjusted to 10 mM azide at pH 8.4 (t/sub 1/2/, 0.38 min). /sup 35/SO/sub 4//sup 2 -/ in pool 1 also rapidly exchanges with unlabeled medium sulfate. Pool 2 is characterized by the slow release of /sup 35/SO/sub 4//sup 2 -/ induced by azide at pH 8.4 or unlabeled sulfate (t/sub 1/2/, 32 to 49 min). Early in the /sup 35/SO/sub 4//sup 2 -/ accumulation process, up to 78% of the total transported substrate is found in pool 1. At equilibrium, pool 1 accounts for only about 2% of the total accumulated /sup 35/SO/sub 4//sup 2 -/. Monensin (33 ..mu..m) accelerates the transfer of /sup 35/SO/sub 4//sup 2 -/ from pool 1 to pool 2. Valinomycin (0.2 ..mu..M) and tetraphynylboron/sup -/ (1 mM) retard the transfer of /sup 35/SO/sub 4//sup 2 -/ from pool 1 to pool 2. Pool 2 may reside in a vacuole or other intracellular organelle. A model for the transfer of sulfate from pool 1 to pool 2 is presented.« less

Testing for handling bias in survival estimation for black brant

USGS Publications Warehouse

Sedinger, J.S.; Lindberg, M.S.; Rexstad, E.A.; Chelgren, N.D.; Ward, D.H.

1997-01-01

We used an ultrastructure approach in program SURVIV to test for, and remove, bias in survival estimates for the year following mass banding of female black brant (Branta bernicla nigricans). We used relative banding-drive size as the independent variable to control for handling effects in our ultrastructure models, which took the form: S = S0(1 - ??D), where ?? was handling effect and D was the ratio of banding-drive size to the largest banding drive. Brant were divided into 3 classes: goslings, initial captures, and recaptures, based on their state at the time of banding, because we anticipated the potential for heterogeneity in model parameters among classes of brant. Among models examined, for which ?? was not constrained, a model with ?? constant across classes of brant and years, constant survival rates among years for initially captured brant but year-specific survival rates for goslings and recaptures, and year- and class-specific detection probabilities had the lowest Akaike Information Criterion (AIC). Handling effect, ??, was -0.47 ?? 0.13 SE, -0.14 ?? 0.057, and -0.12 ?? 0.049 for goslings, initially released adults, and recaptured adults. Gosling annual survival in the first year ranged from 0.738 ?? 0.072 for the 1986 cohort to 0.260 ?? 0.025 for the 1991 cohort. Inclusion of winter observations increased estimates of first-year survival rates by an average of 30%, suggesting that permanent emigration had an important influence on apparent survival, especially for later cohorts. We estimated annual survival for initially captured brant as 0.782 ?? 0.013, while that for recaptures varied from 0.726 ?? 0.034 to 0.900 ?? 0.062. Our analyses failed to detect a negative effect of handling on survival of brant, which is consistent with an hypothesis of substantial inherent heterogeneity in post-fledging survival rates, such that individuals most likely to die as a result of handling also have lower inherent survival probabilities.

Decomposition reaction rate of BCl3-C3H6(propene)-H2 in the gas phase.

PubMed

Xiao, Jun; Su, Kehe; Liu, Yan; Ren, Hongjiang; Zeng, Qingfeng; Cheng, Laifei; Zhang, Litong

2012-07-05

The decomposition reaction rate in the BCl(3)-C(3)H(6)-H(2) gas phase reaction system in preparing boron carbides was investigated based on the most favorable reaction pathways proposed by Jiang et al. [Theor. Chem. Accs. 2010, 127, 519] and Yang et al. [J. Theor. Comput. Chem. 2012, 11, 53]. The rate constants of all the elementary reactions were evaluated with the variational transition state theory. The vibrational frequencies for the stationary points as well as the selected points along the minimum energy paths (MEPs) were calculated with density functional theory at the B3PW91/6-311G(d,p) level and the energies were refined with the accurate model chemistry method G3(MP2). For the elementary reaction associated with a transition state, the MEP was obtained with the intrinsic reaction coordinates, while for the elementary reaction without transition state, the relaxed potential energy surface scan was employed to obtain the MEP. The rate constants were calculated for temperatures within 200-2000 K and fitted into three-parameter Arrhenius expressions. The reaction rates were investigated by using the COMSOL software to solve numerically the coupled differential rate equations. The results show that the reactions are, consistent with the experiments, appropriate at 1100-1500 K with the reaction time of 30 s for 1100 K, 1.5 s for 1200 K, 0.12 s for 1300 K, 0.011 s for 1400 K, or 0.001 s for 1500 K, for propene being almost completely consumed. The completely dissociated species, boron carbides C(3)B, C(2)B, and CB, have very low concentrations, and C(3)B is the main product at higher temperatures, while C(2)B is the main product at lower temperatures. For the reaction time 1 s, all these concentrations approach into a nearly constant. The maximum value (in mol/m(3)) is for the highest temperature 1500 K with the orders of -13, -17, and -23 for C(3)B, C(2)B, and CB, respectively. It was also found that the logarithm of the overall reaction rate and reciprocal temperature have an excellent linear relationship within 700-2000 K with a correlation coefficient of 0.99996. This corresponds to an apparent activation energy 337.0 kJ/mol, which is comparable with the energy barrier 362.6 kJ/mol of the rate control reaction at 0 K but is higher than either of the experiments 208.7 kJ/mol or the Gibbs free energy barrier 226.2 kJ/mol at 1200 K.

Assessing Chemical Retention Process Controls in Ponds

NASA Astrophysics Data System (ADS)

Torgersen, T.; Branco, B.; John, B.

2002-05-01

Small ponds are a ubiquitous component of the landscape and have earned a reputation as effective chemical retention devices. The most common characterization of pond chemical retention is the retention coefficient, Ri= ([Ci]inflow-[Ci] outflow)/[Ci]inflow. However, this parameter varies widely in one pond with time and among ponds. We have re-evaluated literature reported (Borden et al., 1998) monthly average retention coefficients for two ponds in North Carolina. Employing a simple first order model that includes water residence time, the first order process responsible for species removal have been separated from the water residence time over which it acts. Assuming the rate constant for species removal is constant within the pond (arguable at least), the annual average rate constant for species removal is generated. Using the annual mean rate constant for species removal and monthly water residence times results in a significantly enhanced predictive capability for Davis Pond during most months of the year. Predictive ability remains poor in Davis Pond during winter/unstratified periods when internal loading of P and N results in low to negative chemical retention. Predictive ability for Piedmont Pond (which has numerous negative chemical retention periods) is improved but not to the same extent as Davis Pond. In Davis Pond, the rate constant for sediment removal (each month) is faster than the rate constant for water and explains the good predictability for sediment retention. However, the removal rate constant for P and N is slower than the removal rate constant for sediment (longer water column residence time for P,N than for sediment). Thus sedimentation is not an overall control on nutrient retention. Additionally, the removal rate constant for P is slower than for TOC (TOC is not the dominate removal process for P) and N is removed slower than P (different in pond controls). For Piedmont Pond, sediment removal rate constants are slower than the removal rate constant for water indicating significant sediment resuspension episodes. It appears that these sediment resuspension events are aperiodic and control the loading and the chemical retention capability of Piedmont Pond for N,P,TOC. These calculated rate constants reflect the differing internal loading processes for each component and suggest means and mechanisms for the use of ponds in water quality management.

Dynamic Characteristics of The DSI-Type Constant-Flow Valves

NASA Astrophysics Data System (ADS)

Kang, Yuan; Hu, Sheng-Yan; Chou, Hsien-Chin; Lee, Hsing-Han

Constant flow valves have been presented in industrial applications or academic studies, which compensate recess pressures of a hydrostatic bearing to resist load fluctuating. The flow rate of constant-flow valves can be constant in spite of the pressure changes in recesses, however the design parameters must be specified. This paper analyzes the dynamic responses of DSI-type constant-flow valves that is designed as double pistons on both ends of a spool with single feedback of working pressure and regulating restriction at inlet. In this study the static analysis presents the specific relationships among design parameters for constant flow rate and the dynamic analyses give the variations around the constant flow rate as the working pressure fluctuates.

The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California

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

Maher, K.; Steefel, C. I.; White, A.F.

2009-02-25

In order to explore the reasons for the apparent discrepancy between laboratory and field weathering rates and to determine the extent to which weathering rates are controlled by the approach to thermodynamic equilibrium, secondary mineral precipitation and flow rates, a multicomponent reactive transport model (CrunchFlow) was used to interpret soil profile development and mineral precipitation and dissolution rates at the 226 ka marine terrace chronosequence near Santa Cruz, CA. Aqueous compositions, fluid chemistry, transport, and mineral abundances are well characterized (White et al., 2008, GCA) and were used to constrain the reaction rates for the weathering and precipitating minerals inmore » the reactive transport modeling. When primary mineral weathering rates are calculated with either of two experimentally determined rate constants, the nonlinear, parallel rate law formulation of Hellmann and Tisser and [2006] or the aluminum inhibition model proposed by Oelkers et al. [1994], modeling results are consistent with field-scale observations when independently constrained clay precipitation rates are accounted for. Experimental and field rates, therefore, can be reconciled at the Santa Cruz site. Observed maximum clay abundances in the argillic horizons occur at the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO{sub 2}(aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total mass removed from the weathering profile. Our analysis suggests that secondary clay precipitation is as important as aqueous transport in governing the amount of dissolution that occurs within a profile because clay minerals exert a strong control over the reaction affinity of the dissolving primary minerals. The modeling also indicates that the weathering advance rate and the total mass of mineral dissolved is controlled by the thermodynamic saturation of the primary dissolving phases plagioclase and K-feldspar, as is evident from the difference in propagation rates of the reaction fronts for the two minerals despite their very similar kinetic rate laws.« less

Solubility enhancement of dioxins and PCBs by surfactant monomers and micelles quantified with polymer depletion techniques.

PubMed

Schacht, Veronika J; Grant, Sharon C; Escher, Beate I; Hawker, Darryl W; Gaus, Caroline

2016-06-01

Partitioning of super-hydrophobic organic contaminants (SHOCs) to dissolved or colloidal materials such as surfactants can alter their behaviour by enhancing apparent aqueous solubility. Relevant partition constants are, however, challenging to quantify with reasonable accuracy. Partition constants to colloidal surfactants can be measured by introducing a polymer (PDMS) as third phase with known PDMS-water partition constant in combination with the mass balance approach. We quantified partition constants of PCBs and PCDDs (log KOW 5.8-8.3) between water and sodium dodecyl sulphate monomers (KMO) and micelles (KMI). A refined, recently introduced swelling-based polymer loading technique allowed highly precise (4.5-10% RSD) and fast (<24 h) loading of SHOCs into PDMS, and due to the miniaturisation of batch systems equilibrium was reached in <5 days for KMI and <3 weeks for KMO. SHOC losses to experimental surfaces were substantial (8-26%) in monomer solutions, but had a low impact on KMO (0.10-0.16 log units). Log KMO for PCDDs (4.0-5.2) were approximately 2.6 log units lower than respective log KMI, which ranged from 5.2 to 7.0 for PCDDs and 6.6-7.5 for PCBs. The linear relationship between log KMI and log KOW was consistent with more polar and moderately hydrophobic compounds. Apparent solubility increased with increasing hydrophobicity and was highest in micelle solutions. However, this solubility enhancement was also considerable in monomer solutions, up to 200 times for OCDD. Given the pervasive presence of surfactant monomers in typical field scenarios, these data suggest that low surfactant concentrations may be effective long-term facilitators for subsurface transport of SHOCs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Experimental and Estimated Rate Constants for the Reactions of Hydroxyl Radicals with Several Halocarbons

NASA Technical Reports Server (NTRS)

DeMore, W.B.

1996-01-01

Relative rate experiments are used to measure rate constants and temperature dependencies of the reactions of OH with CH3F (41), CH2FCl (31), CH2BrCl (30B1), CH2Br2 (3OB2), CHBr3 (2OB3), CF2BrCHFCl (123aBl(alpha)), and CF2ClCHCl2 (122). Rate constants for additional compounds of these types are estimated using an empirical rate constant estimation method which is based on measured rate constants for a wide range of halocarbons. The experimental data are combined with the estimated and previously reported rate constants to illustrate the effects of F, Cl, and Br substitution on OH rate constants for a series of 19 halomethanes and 25 haloethanes. Application of the estimation technique is further illustrated for some higher hydrofluorocarbons (HFCs), including CHF2CF2CF2CF2H (338pcc), CF3CHFCHFCF2CF3 (43-10mee), CF3CH2CH2CF3 (356ffa), CF3CH2CF2CH2CF3 (458mfcf), CF3CH2CHF2 (245fa), and CF3CH2CF2CH3 (365mfc). The predictions are compared with literature data for these compounds.

Identification and application of ssDNA aptamers against H₃₇Rv in the detection of Mycobacterium tuberculosis.

PubMed

Aimaiti, Rusitanmujiang; Qin, Lianhua; Cao, Ting; Yang, Hua; Wang, Jie; Lu, Junmei; Huang, Xiaochen; Hu, Zhongyi

2015-11-01

Microscopy of direct smear with the Ziehl-Neelsen stain is still broadly used in tuberculosis diagnosis. However, this method suffers from low specificity and is difficult to distinguish Mycobacterium tuberculosis (MTB) from nontuberculosis mycobacterial (NTM), since all mycobacterial species are positive in Ziehl-Neelsen stain. In this study, we utilized whole cell SELEX to obtain species-specific aptamers for increasing the specificity of MTB detection. Whole cell SELEX was performed in MTB reference strain H37Rv by two selection processes based on enzyme-linked plate or Eppendorf tube, respectively. To increase success rate of generating aptamers, the selection processes were systematically monitored to understand the dynamic evolution of aptamers against complex structure of target bacteria. Two preponderant groups and ten high-affinity aptamers were obtained by analyzing the dynamic evolution. Preponderant aptamer MA1 from group I showed relatively high binding affinity with apparent dissociation constant (KD value) of 12.02 nM. Sandwich ELISA assay revealed five aptamer combinations effectively bound MTB strains in preliminary evaluation, especially the combination based on aptamer MA2 (another preponderant aptamer from group II) and MA1. Further evaluated in many other strains, MA2/MA1 combination effectively identified MTB from NTM or other pathogenic bacteria, and displayed the high specificity and sensitivity. Binding analysis of aptamer MA1 or MA2 by fluorescence microscopy observation showed high binding reactivity with H37Rv, low apparent cross-reactivity with M. marinum, and no apparent cross-reactivity with Enterobacter cloacae. Taken together, this study provides attractive candidate species-specific aptamers to effectively capture or discriminate MTB strains.

Population pharmacokinetics of lyophilized recombinant glucagon-like peptide-1 receptor agonist (recombinant exendin-4, rE-4) in Chinese patients with type 2 diabetes mellitus
.

PubMed

Zang, Yan-Nan; Zhang, Min-Jie; Wang, Yi-Tong; Wang, Chen; Wang, Qian; Zheng, Qing-Shan; Ji, Li-Nong; Guo, Wei; Fang, Yi

2017-08-01

To investigate the population pharmacokinetics of lyophilized recombinant glucagon-like peptide-1 receptor agonist (rE-4) in Chinese patients with type 2 diabetes mellitus (T2DM) for plasma concentration estimation and individualized treatment. Twelve patients with T2DM were enrolled to receive subcutaneous injections of rE-4 at 5 µg twice daily for 84 days. Administration dosage was adjusted from 5 µg to 10 µg twice daily at day 29 in case of glycated albumin (GA) ≥ 17%. The population pharmacokinetic model was developed in the nonlinear mixed-effects modeling software NONMEM. The data were best described by a two-compartment model with first-order absorption and elimination. The outcome parameters were as follows: apparent clearance (CL/F) 6.67 L/h, apparent distribution volume of central compartment (V_c/F) 19.4 L, absorption rate constant (K_a) 1.39 h^-1, apparent distribution volume of peripheral compartment (V_p/F) 22.6 L, intercompartmental clearance (Q/F) 1.28 L/h. The interindividual variabilities for CL/F, V_c/F, K_a, and Q/F were 64.4%, 57.7%, 45.5%, and 153.3%, respectively. The intra-individual variability of proportional error model was 41.7%. No covariate was screened out that showed significant influence on the model parameters. The established two-compartment model with first-order absorption and elimination successfully described the pharmacokinetic characteristics of rE-4 in Chinese patients with T2DM.
.

Secondary electron emission influenced by oxidation on the aluminum surface: the roles of the chemisorbed oxygen and the oxide layer

NASA Astrophysics Data System (ADS)

Li, Jiangtao; Hoekstra, Bart; Wang, Zhen-Bin; Qiu, Jie; Pu, Yi-Kang

2018-04-01

A relationship between the apparent secondary electron yield ({γ }{{se}}) and the oxygen coverage/oxide layer thickness on an aluminum cathode is obtained in an experiment under a controlled environment. The apparent secondary electron yield ({γ }{{se}}) is deduced from the breakdown voltage between two parallel plate electrodes in a 360 mTorr argon environment using a simple Townsend breakdown model with the assumption that the variation of the apparent secondary electron yield is dominated by the variation of the argon ion induced processes. The oxygen coverage/oxide layer thickness on the aluminum cathode is measured by a semi in situ x-ray photoemission spectroscopy equipment which is directly attached to the discharge chamber. It is found that three phases exist: (1) in the monomonolayer regime, as the oxygen coverage increases from 0 to 0.3, {γ }{{se}} decreases by nearly 40 % , (2) as the oxygen coverage increases from 0.3 to 1, {γ }{{se}} keeps nearly constant, (3) as the oxide layer thickness increases from about 0.3 nm to about 1.1 nm, {γ }{{se}} increases by 150 % . We propose that, in the submonolayer regime, the chemisorbed oxygen on the aluminum surface causes the decrease of {γ }{{se}} by creating a local potential barrier, which reduces the Auger neutralization rate and the energy gained by the Auger electrons. In the multilayer regime, as the oxide layer grows in thickness, there are three proposed mechanisms which cause the increase of {γ }{{se}}: (1) the work function decreases; (2) resonance neutralization and Auger de-excitation may exist. This is served as another channel for secondary electron production; (3) the kinetic energy of Auger electrons is increased on average, leading to a higher probability for electrons to overcome the surface potential barrier.

On-line coupling of immobilized cytochrome P450 microreactor and capillary electrophoresis: A promising tool for drug development.

PubMed

Schejbal, Jan; Řemínek, Roman; Zeman, Lukáš; Mádr, Aleš; Glatz, Zdeněk

2016-03-11

In this work, the combination of an immobilized enzyme microreactor (IMER) based on the clinically important isoform cytochrome P450 2C9 (CYP2C9) with capillary electrophoresis (CE) is presented. The CYP2C9 was attached to magnetic SiMAG-carboxyl microparticles using the carbodiimide method. The formation of an IMER in the inlet part of the separation capillary was ensured by two permanent magnets fixed in a cassette from the CE apparatus in the repulsive arrangement. The resulting on-line system provides an integration of enzyme reaction mixing and incubation, reaction products separation, detection and quantification into a single fully automated procedure with the possibility of repetitive use of the enzyme and minuscule amounts of reactant consumption. The on-line kinetic and inhibition studies of CYP2C9's reaction with diclofenac as a model substrate and sulfaphenazole as a model inhibitor were conducted in order to demonstrate its practical applicability. Values of the apparent Michalis-Menten constant, apparent maximum reaction velocity, Hill coefficient, apparent inhibition constant and half-maximal inhibition concentration were determined on the basis of the calculation of the effective substrate and inhibitor concentrations inside the capillary IMER using a model described by the Hagen-Poisseulle law and a novel enhanced model that reflects the influence of the reactants' diffusion during the injection process. Copyright © 2016 Elsevier B.V. All rights reserved.

The Multiphase Rheology of Andesitic Magmas from the 1.9ka Eruption of Turrialba Volcano (Costa Rica)

NASA Astrophysics Data System (ADS)

Vona, A.; Di Piazza, A.; Romano, C.; De Astis, G.; Soto, G. J.

2014-12-01

We present a study of high-temperature, uniaxial deformation experiments of natural magma from an andesitic eruption of Turrialba volcano (1.9ka Plinian eruption). The aim of this work is to investigate the multiphase rheology (liquid+vesicles+crystals) of natural samples and the effect of vesicles and crystals on the magma viscosity. The experiments were performed using a high-temperature uniaxial Geocomp LoadTrac II press at dry atmospheric conditions and controlled deformation rates. Cores of natural sample (with Φcrys=0.20-0.30 and Φves=0.41-0.58) were deformed isothermally (790-870°C) at variable strain rates (VSR, from 10-6 to 10-4 s-1) and constant strain rate (CSR, 10-5 s-1). VSR were performed at low total amount of strain (e<0.10) to parameterize the flow behavior of these complex natural materials. The stress-strain rate relationships under flow conditions showed a linear trend between the applied stress and strain rate in the temperature interval investigated. All the samples display a steep linear trend, typical of Newtonian fluids (n index ~ 1), with a very small shear thinning behavior. CSR tests were performed at different total amount of strain (e=0.15-0.25-0.35). Strain hardening was observed with increasing deformation, resulting in an increase of apparent viscosity (up to 100.5 Pa s). This increase is related to the loss of total porosity (up to ΔΦves=0.15) due to compaction of the sample as indicated by post-run analyses . The measured multiphase rheology of Turrialba magmas was compared with literature models for both crystal- and bubble-bearing suspension. We calculate a difference of ~101 Pa s in magma apparent viscosity between high and low density samples, that coupled with a lateral temperature gradient inside the conduit of the volcano, could increase up to ~103 Pa s. The large difference in viscosity could be responsible of significant rheological contrasts, possibly resulting in strain localization and brittle fragmentation of magma.

Accumulation of 2,3,7,8-tetrachlorodibenzo-p-dioxin by rainbow trout (Onchorhynchus mykiss) at environmentally relevant dietary concentrations

USGS Publications Warehouse

Jones, Paul D.; Kannan, Kurunthachalam; Newsted, John L.; Tillitt, Donald E.; Williams, Lisa L.; Giesy, John P.

2001-01-01

Rainbow trout were fed a diet containing 1.8, 18, or 90 pg/g 3H-2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) for up to 320 d. Concentrations of TCDD were determined in muscle, liver, and ovaries at 100, 150, 200, and 250 d. Concentrations of TCDD reached an apparent steady-state concentration in liver after 100 d of exposure, whereas concentrations in other tissues continued to increase until 150 d of exposure. The greatest portion of the total mass of TCDD was present in the muscle tissue with lesser proportions in other organs. As the ovaries developed before spawning, an increase occurred in the total mass of TCDD present in this tissue. The assimilation rate of TCDD during the initial 100 d of the exposure was determined to be between 10 and 30%. This is somewhat less than estimates derived based on both uptake and elimination constants determined during shorter exposures. Biomagnification factors (BMFs) were estimated for all tissues and exposure concentrations, and at all exposure periods. Lipid-normalized BMFs for muscle ranged from 0.38 to 1.51, which is consistent with the value of 1.0 predicted from fugacity theory. Uptake and depuration rate constants were determined and used to predict individual organ TCDD concentrations. Comparison with observed values indicated that the model could be used to predict tissue concentrations from the known concentrations of TCDD in food. This model will allow more refined risk assessments by predicting TCDD concentrations in sensitive tissues such as developing eggs.

Direct measurement of asperity contact growth in quartz at hydrothermal conditions

USGS Publications Warehouse

Beeler, Nicholas M.; Hickman, Stephen H.

2015-01-01

Earthquake recurrence requires interseismic fault restrengthening which results from solid state deformation in room-temperature friction and indentation experiments. In contrast exhumed fault zones show solution-transport processes such as pressure solution and contact overgrowths influence fault zone properties . In the absence of fluid flow, overgrowths are driven by gradients in surface curvature where material is dissolved, diffuses, and precipitates at the contact without convergence normal to the contact. To determine the rate of overgrowth for quartz, we conducted single contact experiments in an externally heated pressure vessel. Convergence was continuously monitored using reflected-light interferometry through a long-working-distance microscope. Contact normal force was constant with an initial effective normal stress of 1.7 MPa, temperature was between 350 and 530{degree sign}C, and water pressure was constant at 150 MPa. Two control experiments were conducted: one dry at 425{degree sign}C and one bi-material (sapphire) at 425{degree sign}C and 150 MPa water pressure. No contact growth or convergence was observed in the controls. For wet single-phase contacts, growth was initially rapid and then decreased with time. No convergence was observed. Fluid inclusions indicate that the contact is not uniformly wetted. The contact is bounded by small regions of high aperture, reflecting local free-face dissolution as the source for the overgrowth. The apparent activation energy is ~125 kJ/mol. Extrapolation predicts rates of contact area increase orders of magnitude faster than in dry, room-temperature and hydrothermal friction experiments, suggesting that natural strength recovery near the base of the seismogenic zone could be dominated by contact overgrowth.

Soil slurry reactors for the assessment of contaminant biodegradation

NASA Astrophysics Data System (ADS)

Toscano, G.; Colarieti, M. L.; Greco, G.

2012-04-01

Slurry reactors are frequently used in the assessment of feasibility of biodegradation in natural soil systems. The rate of contaminant removal is usually quantified by zero- or first-order kinetics decay constants. The significance of such constants for the evaluation of removal rate in the field could be questioned because the slurry reactor is a water-saturated, well-stirred system without resemblance with an unsaturated fixed bed of soil. Nevertheless, a kinetic study with soil slurry reactors can still be useful by means of only slightly more sophisticated kinetic models than zero-/first-order decay. The use of kinetic models taking into account the role of degrading biomass, even in the absence of reliable experimental methods for its quantification, provides further insight into the effect of nutrient additions. A real acceleration of biodegradation processes is obtained only when the degrading biomass is in the growth condition. The apparent change in contaminant removal course can be useful to diagnose biomass growth without direct biomass measurement. Even though molecular biology techniques are effective to assess the presence of potentially degrading microorganism in a "viable-but-nonculturable" state, the attainment of conditions for growth is still important to the development of enhanced remediation techniques. The methodology is illustrated with reference to data gathered for two test sites, Oslo airport Gardermoen in Norway (continuous contamination by aircraft deicing fluids) and the Trecate site in Italy (aged contamination by crude oil spill). This research is part of SoilCAM project (Soil Contamination, Advanced integrated characterisation and time-lapse Monitoring 2008-2012, EU-FP7).

Perfluorinated Surfactant Chain-Length Effects on Sonochemical Kinetics

NASA Astrophysics Data System (ADS)

Campbell, Tammy Y.; Vecitis, Chad D.; Mader, Brian T.; Hoffmann, Michael R.

2009-08-01

The sonochemical degradation kinetics of the aqueous perfluorochemicals (PFCs) perfluorobutanoate (PFBA), perfluorobutanesulfonate (PFBS), perfluorohexanoate (PFHA), and perfluorohexanesulfonate (PFHS) have been investigated. Surface tension measurements were used to evaluate chain-length effects on equilibrium air-water interface partitioning. The PFC air-water interface partitioning coefficients, KeqPF, and maximum surface concentrations, ΓmaxPF, were determined from the surface pressure equation of state for PFBA, PFBS, PFHA, and PFHS. Relative KeqPF values were dependent upon chain length KeqPFHS ≅ 2.1KeqPFHA ≅ 3.9KeqPFBS ≅ 5.0KeqPFBA, whereas relative ΓmaxPF values had minimal chain length dependence ΓmaxPFHS ≅ ΓmaxPFHA ≅ ΓmaxPFBS ≅ 2.2ΓmaxPFBA. The rates of sonolytic degradation were determined over a range of frequencies from 202 to 1060 kHz at dilute (<1 μM) initial PFC concentrations and are compared to previously reported results for their C8 analogs: perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA). Under all conditions, the time-dependent PFC sonolytic degradation was observed to follow pseudo-first-order kinetics, i.e., below kinetic saturation, suggesting bubble-water interface populations were significantly below the adsorption maximum. The PFHX (where X = A or S) sonolysis rate constant was observed to peak at an ultrasonic frequency of 358 kHz, similar to that for PFOX. In contrast, the PFBX degradation rate constants had an apparent maximum at 610 kHz. Degradation rates observed for PFHX are similar to previously determined PFOX rates, kapp,358PFOX ≅ kapp,358PFHX. PFOX is sonolytically pyrolyzed at the transiently cavitating bubble-water interface, suggesting that rates should be proportional to equilibrium interfacial partitioning. However, relative equilibrium air-water interfacial partitioning predicts that KeqPFOX ≅ 5KeqPFHX. This suggests that at dilute PFC concentrations, adsorption to the bubble-water interface is ultrasonically enhanced due to high-velocity radial bubble oscillations. PFC sonochemical kinetics are slower for PFBS and further diminished for PFBA as compared to longer analogs, suggesting that PFBX surface films are of lower stability due to their greater water solubility.

Accounting for orphaned aftershocks in the earthquake background rate

USGS Publications Warehouse

Van Der Elst, Nicholas

2017-01-01

Aftershocks often occur within cascades of triggered seismicity in which each generation of aftershocks triggers an additional generation, and so on. The rate of earthquakes in any particular generation follows Omori's law, going approximately as 1/t. This function decays rapidly, but is heavy-tailed, and aftershock sequences may persist for long times at a rate that is difficult to discriminate from background. It is likely that some apparently spontaneous earthquakes in the observational catalogue are orphaned aftershocks of long-past main shocks. To assess the relative proportion of orphaned aftershocks in the apparent background rate, I develop an extension of the ETAS model that explicitly includes the expected contribution of orphaned aftershocks to the apparent background rate. Applying this model to California, I find that the apparent background rate can be almost entirely attributed to orphaned aftershocks, depending on the assumed duration of an aftershock sequence. This implies an earthquake cascade with a branching ratio (the average number of directly triggered aftershocks per main shock) of nearly unity. In physical terms, this implies that very few earthquakes are completely isolated from the perturbing effects of other earthquakes within the fault system. Accounting for orphaned aftershocks in the ETAS model gives more accurate estimates of the true background rate, and more realistic expectations for long-term seismicity patterns.

Accounting for orphaned aftershocks in the earthquake background rate

NASA Astrophysics Data System (ADS)

van der Elst, Nicholas J.

2017-11-01

Aftershocks often occur within cascades of triggered seismicity in which each generation of aftershocks triggers an additional generation, and so on. The rate of earthquakes in any particular generation follows Omori's law, going approximately as 1/t. This function decays rapidly, but is heavy-tailed, and aftershock sequences may persist for long times at a rate that is difficult to discriminate from background. It is likely that some apparently spontaneous earthquakes in the observational catalogue are orphaned aftershocks of long-past main shocks. To assess the relative proportion of orphaned aftershocks in the apparent background rate, I develop an extension of the ETAS model that explicitly includes the expected contribution of orphaned aftershocks to the apparent background rate. Applying this model to California, I find that the apparent background rate can be almost entirely attributed to orphaned aftershocks, depending on the assumed duration of an aftershock sequence. This implies an earthquake cascade with a branching ratio (the average number of directly triggered aftershocks per main shock) of nearly unity. In physical terms, this implies that very few earthquakes are completely isolated from the perturbing effects of other earthquakes within the fault system. Accounting for orphaned aftershocks in the ETAS model gives more accurate estimates of the true background rate, and more realistic expectations for long-term seismicity patterns.

Oligonucleotide facilitators may inhibit or activate a hammerhead ribozyme.

PubMed Central

Jankowsky, E; Schwenzer, B

1996-01-01

Facilitators are oligonucleotides capable of affecting hammerhead ribozyme activity by interacting with the substrate at the termini of the ribozyme. Facilitator effects were determined in vitro using a system consisting of a ribozyme with 7 nucleotides in every stem sequence and two substrates with inverted facilitator binding sequences. The effects of 9mer and 12mer RNA as well as DNA facilitators which bind either adjacent to the 3'- or 5'-end of the ribozyme were investigated. A kinetic model was developed which allows determination of the apparent dissociation constant of the ribozyme-substrate complex from single turnover reactions. We observed a decreased dissociation constant of the ribozyme-substrate complex due to facilitator addition corresponding to an additional stabilization energy of delta delta G=-1.7 kcal/mol with 3'-end facilitators. The cleavage rate constant was increased by 3'-end facilitators and decreased by 5'-end facilitators. Values for Km were slightly lowered by all facilitators and kcat was increased by 3'-end facilitators and decreased by 5'-end facilitators in our system. Generally the facilitator effects increased with the length of the facilitators and RNA provided greater effects than DNA of the same sequence. Results suggest facilitator influences on several steps of the hammerhead reaction, substrate association, cleavage and dissociation of products. Moreover, these effects are dependent in different manners on ribozyme and substrate concentration. This leads to the conclusion that there is a concentration dependence whether activation or inhibition is caused by facilitators. Conclusions are drawn with regard to the design of hammerhead ribozyme facilitator systems. PMID:8602353

Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

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

Soudackov, Alexander V.; Hammes-Schiffer, Sharon

2015-11-21

Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at highmore » temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton transfer and proton-coupled electron transfer in chemical and biological processes.« less

Spatio-temporal scaling of channels in braided streams.

Treesearch

A.G. Hunt; G.E. Grant; V.K. Gupta

2006-01-01

The spatio-temporal scaling relationship for individual channels in braided streams is shown to be identical to the spatio-temporal scaling associated with constant Froude number, e.g., Fr = l. A means to derive this relationship is developed from a new theory of sediment transport. The mechanism by which the Fr = l condition apparently governs the scaling seems to...

Direct sensing of fluoride in aqueous solutions using a boronic acid based sensor.

PubMed

Wu, Xin; Chen, Xuan-Xuan; Song, Bing-Nan; Huang, Yan-Jun; Ouyang, Wen-Juan; Li, Zhao; James, Tony D; Jiang, Yun-Bao

2014-11-21

Binding of the fluoride ion triggers aggregation of a pyreneboronic acid-catechol ensemble in acidic aqueous solutions, giving rise to intense excimer emission, allowing for sensitive fluoride ion sensing at ppm levels, with an apparent fluoride binding constant higher than 10(3) M(-1) which is unprecedented for boronic acid sensors in water.

Two Curriculum-Relevant/Open Day Physics Experiments Concerning Gravity

ERIC Educational Resources Information Center

Sosabowski, Michael Hal; Young, Clive; Matkin, Judy; Ponikwer, Fiona

2013-01-01

Gravity is an intangible abstract force when considered theoretically and yet we are affected by it constantly. The apparently "strong" nature of gravity, which in the layperson's mind causes him or her to stick to the Earth, is belied by the fact that it is the weakest of the fundamental forces. Demonstrations that allow pupils,…

Age-specific survival estimates of King Eiders derived from satellite telemetry

USGS Publications Warehouse

Oppel, Steffen; Powell, Abby N.

2010-01-01

Age- and sex-specific survival and dispersal are important components in the dynamics and genetic structure of bird populations. For many avian taxa survival rates at the adult and juvenile life stages differ, but in long-lived species juveniles' survival is logistically challenging to study. We present the first estimates of hatch-year annual survival rates for a sea duck, the King Eider (Somateria spectabilis), estimated from satellite telemetry. From 2006 to 2008 we equipped pre-fiedging King Eiders with satellite transmitters on breeding grounds in Alaska and estimated annual survival rates during their first 2 years of life with known-fate models. We compared those estimates to survival rates of adults marked in the same area from 2002 to 2008. Hatch-year survival varied by season during the first year of life, and model-averaged annual survival rate was 0.67 (95% CI: 0.48–0.80). We did not record any mortality during the second year and were therefore unable to estimate second-year survival rate. Adults' survival rate was constant through the year (0.94, 95% CI: 0.86–0.97). No birds appeared to breed during their second summer. While 88% of females with an active transmitter (n = 9) returned to their natal area at the age of 2 years, none of the 2-year old males (n = 3) did. This pattern indicates that females' natal philopatry is high and suggests that males' higher rates of dispersal may account for sex-specific differences in apparent survival rates of juvenile sea ducks when estimated with mark—recapture methods.

Transient rheology of crystallizing andesitic magmas

NASA Astrophysics Data System (ADS)

de Biasi, L. J.; Chevrel, M. O.; Hanson, J. B.; Cimarelli, C.; Lavallée, Y.; Dingwell, D. B.

2012-04-01

The viscosity of magma strongly influences its rheological behaviour, which is a key determinant of magma transport processes and volcanic eruptions. Understanding the factors controlling the viscosity of magma is important to our assessment of hazards posed by active volcanoes. In nature, magmas span a very wide range in viscosity (10-1 to 1014 Pa s), depending on chemical composition (including volatile content), temperature, and importantly, crystal fraction, which further induces a complex strain rate dependence (i.e. non-Newtonian rheology). Here, we present results of transient viscosities of a crystallizing andesitic melt (57 wt.% SiO2) from Tungurahua volcano (Ecuador). We followed the experimental method developed by Vona et al. (2011) for the concentric cylinder apparatus, but optimized its implementation by leaving the spindle in situ before quenching the experimental products, to preserve the complete developed texture of the sample. The viscosity is investigated under super-liquidus (1400 ° C) and sub-liquidus temperatures (1162 and 1167 ° C). For each temperature increment, thermal equilibrium is achieved over a period of days while the spindle constantly stirs the magma. Simultaneous monitoring of the torque is used to calculate the apparent viscosity of the transient suspension. To get a better understanding of the nucleation and crystal growth processes that are involved at sub-liquidus conditions, further time-step experiments were carried out, where the samples were quenched at various equilibration stages. The mineralogical assemblage, as well as the crystal fraction, distribution and preferential alignment were then quantitatively analyzed. At temperatures below the liquidus, the suspension shows a progressive, but irregular increase of the relative shear viscosity. First, the viscosity slightly increases, possibly due to the crystallization of small, equant oxides and the formation of plagioclase nuclei. After some time (1.5-2.5 days), crystallization of large, tabular plagioclase begins, inducing a significantly stronger increase in apparent viscosity until thermo-chemical equilibration is achieved. After continued stirring the apparent viscosity slightly decreases, likely due to increasing crystal alignment. The analysis of pre-equilibrium quenched samples indicates that crystals nucleate and grow preferentially in proximity to both the spindle and the crucible wall. Furthermore, decreasing the stirring rate (aka strain rate) results in an increase in the apparent viscosity, which evidences the non-Newtonian characteristics of the magmatic suspension. In conclusion, these experiments indicate that natural andesitic magmas undergo significant rheological changes at the onset of crystallization. The observed thermo-chemical variations elucidate a transient viscosity, which deserves consideration into all problems of magma transport. Reference: Vona, A., Romano, C., Dingwell, D.B., Giordano, D. 2011. The rheology of crystal-bearing basaltic magmas from Stromboli and Etna. Geochim. Cosmochim. Acta, 75, 3214-3236.

GROUND WATER ISSUE - CALCULATION AND USE OF FIRST-ORDER RATE CONSTANTS FOR MONITORED NATURAL ATTENUATION STUDIES

EPA Science Inventory

This issue paper explains when and how to apply first-order attenuation rate constant calculations in monitored natural attenuation (MNA) studies. First-order attenuation rate constant calculations can be an important tool for evaluating natural attenuation processes at ground-wa...

Trends in electron-ion dissociative recombination of benzene analogs with functional group substitutions: Negative Hammett σpara values

NASA Astrophysics Data System (ADS)

Osborne, David; Lawson, Patrick Andrew; Adams, Nigel; Dotan, Itzhak

2014-06-01

An in-depth study of the effects of functional group substitution on benzene's electron-ion dissociative recombination (e-IDR) rate constant has been conducted. The e-IDR rate constants for benzene, biphenyl, toluene, ethylbenzene, anisole, phenol, and aniline have been measured using a Flowing Afterglow equipped with an electrostatic Langmuir probe (FALP). These measurements have been made over a series of temperatures from 300 to 550 K. A relationship between the Hammett σpara values for each compound and rate constant has indicated a trend in the e-IDR rate constants and possibly in their temperature dependence data. The Hammett σpara value is a method to describe the effect a functional group substituted to a benzene ring has upon the reaction rate constant.

Alternatives to an extended Kalman Filter for target image tracking

NASA Astrophysics Data System (ADS)

Leuthauser, P. R.

1981-12-01

Four alternative filters are compared to an extended Kalman filter (EKF) algorithm for tracking a distributed (elliptical) source target in a closed loop tracking problem, using outputs from a forward looking (FLIR) sensor as measurements. These were (1) an EKF with (second order) bias correction term, (2) a constant gain EKF, (3) a constant gain EKF with bias correction term, and (4) a statistically linearized filter. Estimates are made of both actual target motion and of apparent motion due to atmospheric jitter. These alternative designs are considered specifically to address some of the significant biases exhibited by an EKF due to initial acquisition difficulties, unmodelled maneuvering by the target, low signal-to-noise ratio, and real world conditions varying significantly from those assumed in the filter design (robustness). Filter performance was determined with a Monte Carlo study under both ideal and non ideal conditions for tracking targets on a constant velocity cross range path, and during constant acceleration turns of 5G, 10G, and 20G.

Characterization of Receptor Binding Profiles of Influenza A Viruses Using An Ellipsometry-Based Label-Free Glycan Microarray Assay Platform

PubMed Central

Fei, Yiyan; Sun, Yung-Shin; Li, Yanhong; Yu, Hai; Lau, Kam; Landry, James P.; Luo, Zeng; Baumgarth, Nicole; Chen, Xi; Zhu, Xiangdong

2015-01-01

A key step leading to influenza viral infection is the highly specific binding of a viral spike protein, hemagglutinin (HA), with an extracellular glycan receptor of a host cell. Detailed and timely characterization of virus-receptor binding profiles may be used to evaluate and track the pandemic potential of an influenza virus strain. We demonstrate a label-free glycan microarray assay platform for acquiring influenza virus binding profiles against a wide variety of glycan receptors. By immobilizing biotinylated receptors on a streptavidin-functionalized solid surface, we measured binding curves of five influenza A virus strains with 24 glycans of diverse structures and used the apparent equilibrium dissociation constants (avidity constants, 10–100 pM) as characterizing parameters of viral receptor profiles. Furthermore by measuring binding kinetic constants of solution-phase glycans to immobilized viruses, we confirmed that the glycan-HA affinity constant is in the range of 10 mM and the reaction is enthalpy-driven. PMID:26193329

Characterization of Receptor Binding Profiles of Influenza A Viruses Using An Ellipsometry-Based Label-Free Glycan Microarray Assay Platform.

PubMed

Fei, Yiyan; Sun, Yung-Shin; Li, Yanhong; Yu, Hai; Lau, Kam; Landry, James P; Luo, Zeng; Baumgarth, Nicole; Chen, Xi; Zhu, Xiangdong

2015-07-16

A key step leading to influenza viral infection is the highly specific binding of a viral spike protein, hemagglutinin (HA), with an extracellular glycan receptor of a host cell. Detailed and timely characterization of virus-receptor binding profiles may be used to evaluate and track the pandemic potential of an influenza virus strain. We demonstrate a label-free glycan microarray assay platform for acquiring influenza virus binding profiles against a wide variety of glycan receptors. By immobilizing biotinylated receptors on a streptavidin-functionalized solid surface, we measured binding curves of five influenza A virus strains with 24 glycans of diverse structures and used the apparent equilibrium dissociation constants (avidity constants, 10-100 pM) as characterizing parameters of viral receptor profiles. Furthermore by measuring binding kinetic constants of solution-phase glycans to immobilized viruses, we confirmed that the glycan-HA affinity constant is in the range of 10 mM and the reaction is enthalpy-driven.

Modeling of Anaerobic Digestion with a Focus on Estimation of Hydrolysis Constants at 35, 55, and 60 °C.

PubMed

Haghighatafshar, Salar; Ossiansson, Elin; Koch, Konrad; Kjerstadius, Hamse; Jansen, Jes la Cour; Davidsson, Åsa

2015-07-01

Hydrolysis constants of mixed sludge at 35, 55, and 60 °C were found to be 0.32, 0.44, and 0.50 1/d, respectively, in pilot-scale, semicontinuously operated anaerobic digesters. The hydrolysis constants and estimated chemical oxygen demand fractions in the feed were introduced to a mathematical model for anaerobic digestion published by Siegrist et al. (2002), which is similar to Anaerobic Digestion Model No. 1. First-order and Monod-type kinetics were tested for estimation of hydrolysis constants. The applied kinetics were found to affect the outcome of the regression study. Moreover, the free ammonia inhibition model was excluded for both propionate oxidation and acetate conversion, thanks to the apparent acclimatized biomass. No substantial accumulation of volatile fatty acids was observed in the reactors at 35, 55, and 60 °C, corresponding to free ammonia nitrogen concentrations of about 20, 110, and 130 g N/m³, respectively.

Spectroscopic analyses and studies on respective interaction of cyanuric acid and uric acid with bovine serum albumin and melamine

NASA Astrophysics Data System (ADS)

Chen, Dandan; Wu, Qiong; Wang, Jun; Wang, Qi; Qiao, Heng

2015-01-01

In this work, the fluorescence quenching was used to study the interaction of cyanuric acid (CYA) and uric acid (UA) with bovine serum albumin (BSA) at two different temperatures (283 K and 310 K). The bimolecular quenching constant (Kq), apparent quenching constant (Ksv), effective binding constant (KA) and corresponding dissociation constant (KD), binding site number (n) and binding distance (r) were calculated by adopting Stern-Volmer, Lineweaver-Burk, Double logarithm and overlap integral equations. The results show that CYA and UA are both able to obviously bind to BSA, but the binding strength order is BSA + CYA < BSA + UA. And then, the interactions of CYA and UA with melamine (MEL) under the same conditions were also studied by using similar methods. The results indicates that both CYA and UA can bind together closely with melamine (MEL). It is wished that these research results would facilitate the understanding the formation of kidney stones and gout in the body after ingesting excess MEL.

Glucose biosensing using glassy carbon electrode modified with polyhydroxy-C60, glucose oxidase and ionic-liquid.

PubMed

Yang, Tian; Yang, Xiao-Lu; Zhang, Yu-Shuai; Xiao, BaoLin; Hong, Jun

2014-01-01

Direct electrochemistry of glucose oxidase (GOD) was achieved when an ionic liquid/GOD-Polyhydroxy-C60 functional membrane was confined on a glassy carbon electrode (GCE). The cyclic voltammograms (CVs) of the modified GCE showed a pair of redox peaks with a formal potential (E°') of - 329 ± 2 mV. The heterogeneous electron transfer constant (k(s)) was 1.43 s-1. The modified GCE response to glucose was linear in the range from 0.02 to 2.0 mM. The detection limit was 1 μM. The apparent Michaelis-Menten constant (K(m)(app)) was 1.45 mM.

Kinetics of Reduction of CaO-FeO x -MgO-PbO-SiO2 Slags by CO-CO2 Gas Mixtures

NASA Astrophysics Data System (ADS)

Jahanshahi, Sharif; Wright, Steven

2017-08-01

Kinetics of the reaction of lead slags (PbO-CaO-SiO2-FeO x -MgO) with CO-CO2 gas mixtures was studied by monitoring the changes in the slag composition when a stream of CO-CO2 gas mixture was blown on the surface of thin layers of slags (3 to 10 mm) at temperatures in the range of 1453 K to 1593 K (1180 °C to 1320 °C). These measurements were carried out under conditions where mass transfer in the gas phase was not the rate-limiting step and the reduction rates were insensitive to factors affecting mass transfer in the slag phase. The results show simultaneous reduction of PbO and Fe2O3 in the slag. The measured specific rate of oxygen removal from the melts varied from about 1 × 10-6 to 4 × 10-5 mol O cm-2 s-1 and was strongly dependent on the slag chemistry and its oxidation state, partial pressure of CO in the reaction gas mixture, and temperature. The deduced apparent first-order rate constant increased with increasing iron oxide content, oxidation state of the slag, and temperature. The results indicate that under the employed experimental conditions, the rate of formation of CO2 at the gas-slag interface is likely to be the rate-limiting step.

Effects of enzyme supplementation on the nutrient, amino acid, and energy utilization efficiency of citrus pulp and hawthorn pulp in Linwu ducks.

PubMed

Zhang, Xu; Li, Haobang; Jiang, Guitao; Wang, Xiangrong; Huang, Xuan; Li, Chuang; Wu, Duanqin; Dai, Qiuzhong

2018-04-11

The objective of this study was to evaluate the effects of enzyme supplementation on the nutrient, amino acid, and energy utilization efficiency of citrus pulp and hawthorn pulp as unusual feedstuffs in Linwu ducks. Forty ducks were assigned to each treatment group and fed diets with or without complex enzyme supplementation. All birds received the same quantity of raw material (60 g) via the force-feeding procedure. With the exception of leucine and phenylalanine, amino acid concentrations in hawthorn pulp were twice those in citrus pulp. Enzyme supplementation significantly increased apparent dry matter digestibility (ADM) of citrus pulp (P < 0.05), but had no significant effects (P > 0.05) on the apparent and true utilization rates of other nutrients, apparent metabolizable energy (AME), or true metabolizable energy (TME), from citrus pulp and hawthorn pulp by Linwu ducks. However, enzyme supplementation significantly increased (P < 0.05) apparent gross energy, true gross energy, AME, and TME of hawthorn pulp for Linwu ducks. There were no differences in the apparent and true utilization rates of amino acids from citrus pulp (P > 0.56) between the groups, with the exception of arginine (P < 0.05). There was an increasing trend in the apparent and true utilization rates of alanine (P = 0.06) and tyrosine (P = 0.074) from citrus pulp with enzyme supplementation. The apparent and true utilization rates of threonine in hawthorn pulp were increased significantly (P < 0.05) following enzyme supplementation. The addition of exogenous enzymes improved the forage quality of citrus pulp and hawthorn pulp, which represent potential feed resources for husbandry production.

Final Technical Report- Radiation Hard Tight Pitch GaInP SPAD Arrays for High Energy Physics

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

Harmon, Eric S.

The specialized photodetectors used in high energy physics experiments often need to remain extremely sensitive for years despite radiation induced damage caused by the constant bombardment of high energy particles. To solve this problem, LightSpin Technologies, Inc. in collaboration with Prof. Bradley Cox and the University of Virginia is developing radiation-hard GaInP photodetectors which are projected to be extraordinarily radiation hard, theoretically capable of withstanding a 100,000-fold higher radiation dose than silicon. In this Phase I SBIR project, LightSpin investigated the performance and radiation hardness of fifth generation GaInP SPAD arrays. These fifth generation devices used a new planar processingmore » approach that enables very tight pitch arrays to be produced. High performance devices with SPAD pitches of 11, 15, and 25 μm were successfully demonstrated, which greatly increased the dynamic range and maximum count rate of the devices. High maximum count rates are critical when considering radiation hardness, since radiation damage causes a proportional increase in the dark count rate, causing SPAD arrays with low maximum count rates (large SPAD pitches) to fail. These GaInP SPAD array Photomultiplier Chips™ were irradiated with protons, electrons, and neutrons. Initial irradiation results were disappointing, with the post-irradiation devices exhibiting excessively high dark currents. The degradation was traced to surface leakage currents that were largely eliminated through the use of trenches etched around the exterior of the Photomultiplier Chip™ (not between SPAD elements). A second round of irradiations on Photomultiplier Chips™ with trenches proved substantially more successful, with post-irradiation dark currents remaining relatively low, though dark count rates were observed to increase at the highest doses. Preliminary analysis of the post-irradiation devices is promising … many of the irradiated Photomultiplier Chips™ still exhibit good gain characteristics after 1E12/cm 2 – 1E13/cm 2 doses and have apparent dark count rates that are lower than the apparent dark count rates published for irradiation of silicon SPAD arrays (silicon photomultipliers or SiPMs). Some post-irradiation results are still pending because the samples will still too radioactive to be shipped back from the irradiation facility for post-irradiation testing.« less

18O/16O in CO2 evolved from goethite during some unusually rapid solid state α-FeOOH to α-Fe2O3 phase transitions: Test of an exchange model for possible use in oxygen isotope analyses of goethite

NASA Astrophysics Data System (ADS)

Yapp, Crayton J.

2015-12-01

The initial ∼60% of an isothermal vacuum dehydration of goethite can commonly be approximated by first order kinetics. Also, natural goethites contain small amounts of an Fe(CO3)OH component in apparent solid solution. The 18O/16O of CO2 evolved from the Fe(CO3)OH during isothermal vacuum dehydrations is related to the 18O/16O of the goethite by an apparent fractionation factor (αapp) that is, in turn, correlated with a first order rate constant, |m|. A kinetic exchange model predicts that αapp should decrease as |m| increases for a range of |m| that corresponds to relatively slow rates of dehydration. This pattern has been observed in published results. In contrast, for rapid rates of dehydration, αapp is predicted to increase with increasing |m|. Isothermal vacuum dehydrations of two natural goethites had unusually large values of |m| and provided serendipitous tests of this rapid-rate prediction. For these experiments, the measured values of αapp were consistent with patterns of variation predicted by the model. This allowed an estimate of the activation energy (E2) of a model parameter, K2, which is the rate constant for oxygen isotope exchange between CO2 and H2O during the solid-state goethite to hematite phase transition. The estimated value of E2 is only ∼9 kJ/mol. Heterogeneous catalysis tends to decrease the activation energies of gas reactions. Consequently, the inferred value of E2 suggests that goethite and/or hematite catalyze oxygen isotope exchange between CO2 and H2O during the solid-state phase change. Yield, δ13C, and δ18O values are routinely measured for increments of CO2 evolved from the Fe(CO3)OH component during isothermal vacuum dehydration of goethite. Model-predicted values of αapp can be combined with plateau δ18O values of the evolved CO2 to estimate the δ18O of the goethite with a less than optimal, but potentially useful, precision of about ±0.8‰. Therefore, a single analytical procedure (incremental dehydration) applied to one aliquot of a sample could provide not only δ13C and mole fractions (X) of the Fe(CO3)OH component, but also hydrogen yield, δD, and the approximate δ18O value of the goethite. Recovery of multiple types of geochemical data from a single aliquot would be particularly useful if the amount of sample available for analysis were limited. Also, the method could be used to estimate the δ18O value of goethite in mixtures of minerals not amenable to selective dissolution - e.g., goethite admixed with hematite.

The influence of baseline severity on efficacy of escitalopram and citalopram in the treatment of major depressive disorder: an extended analysis.

PubMed

Lam, R W; Andersen, H F

2006-09-01

To determine the differences between escitalopram and citalopram in the treatment of patients with major depressive disorder across a range of baseline severity of depression using trend analysis. Data from the three placebo-controlled studies comparing escitalopram to citalopram were analyzed. The pre-specified primary outcome variable was MADRS total score; secondary outcomes included Clinical Global Impression-Severity (CGI-S) and -Improvement (CGI-I) scores. All analyses were based on an intent-to-treat (ITT) population and all direct comparisons were done by ANCOVA adjusting for baseline value and centre. Analyses of the pooled data (N=1203) show that, while the difference between citalopram and placebo was approximately constant across the range of baseline severity, the difference between escitalopram and placebo (p=0.0010 for no trend) and between escitalopram and citalopram (p=0.0012 for no trend) became greater, the more severely depressed the patients were at baseline. A similar pattern was apparent with the CGI-S and CGI-I results. There was a significant superiority of escitalopram over citalopram in response rate (defined as > or = 50% decrease in MADRS total score), and this difference increased with increasing baseline severity. These trend analyses thus indicate that the superiority of escitalopram over citalopram is more apparent as the baseline severity of depression increases.

STUDIES WITH THE ELECTROCARDIOGRAPH ON THE ACTION OF THE VAGUS NERVE ON THE HUMAN HEART

PubMed Central

Robinson, G. Canby; Draper, George

1911-01-01

In hearts showing auricular fibrillation mechanical stimulation of the right vagus nerve causes, as a rule, marked slowing or stoppage of ventricular rhythm, without producing any appreciable effect in the electrocardiographic record of the auricular fibrillation. The ventricular pauses are apparently due to the blocking of stimuli from the auricles. The force of ventricular systole is distinctly weakened for several beats after vagus stimulation, and ectopic ventricular systoles have been seen in several instances, apparently the result of the vagus action. There may, in some cases, be lowered excitability of the ventricles, while no constant change is seen in the size of the electrical complexes representing ventricular systole. PMID:19867466

Correlated patterns in hydrothermal plume distribution and apparent magmatic budget along 2500 km of the Southeast Indian Ridge

USGS Publications Warehouse

Baker, Edward; Christophe Hémond,; Anne Briais,; Marcia Maia,; Scheirer, Daniel S.; Sharon L. Walker,; Tingting Wang,; Yongshun John Chen,

2014-01-01

Multiple geological processes affect the distribution of hydrothermal venting along a mid-ocean ridge. Deciphering the role of a specific process is often frustrated by simultaneous changes in other influences. Here we take advantage of the almost constant spreading rate (65–71 mm/yr) along 2500 km of the Southeast Indian Ridge (SEIR) between 77°E and 99°E to examine the spatial density of hydrothermal venting relative to regional and segment-scale changes in the apparent magmatic budget. We use 227 vertical profiles of light backscatter and (on 41 profiles) oxidation-reduction potential along 27 first and second-order ridge segments on and adjacent to the Amsterdam-St. Paul (ASP) Plateau to map ph, the fraction of casts detecting a plume. At the regional scale, venting on the five segments crossing the magma-thickened hot spot plateau is almost entirely suppressed (ph = 0.02). Conversely, the combined ph (0.34) from all other segments follows the global trend of ph versus spreading rate. Off the ASP Plateau, multisegment trends in ph track trends in the regional axial depth, high where regional depth increases and low where it decreases. At the individual segment scale, a robust correlation between ph and cross-axis inflation for first-order segments shows that different magmatic budgets among first-order segments are expressed as different levels of hydrothermal spatial density. This correlation is absent among second-order segments. Eighty-five percent of the plumes occur in eight clusters totaling ∼350 km. We hypothesize that these clusters are a minimum estimate of the length of axial melt lenses underlying this section of the SEIR.

Physical and biochemical energy balance during an isometric tetanus and steady state recovery in frog sartorius at 0 degree C

PubMed Central

1983-01-01

Frog sartorius muscle stimulated isometrically for 3 s every 256 s to attain a steady state in which initial heat (QI), recovery heat (QR), rate of O2 consumption (JO2), and isometric force (PO) generated are constant for each cycle. For a 3-s tetanus given every 256 s, JO2 was 0.106 mumol/(min . g blotted weight), approximately 71% of the maximum rate observed, whereas lactate production was negligible under these conditions. QI, QT(= QI + QR), and QT/QI were 88.2, 181.5, 2.06 mJ/g blotted weight, respectively. The high-energy phosphate breakdown (delta approximately P) breakdown during the first 3-s tetanus was not different from that during a contraction in the steady state and averaged 1.1 mumol/g blotted weight. Less than half of the initial heat could be accounted for in terms of the extent of the known chemical reactions occurring during contraction. From the stoichiometry of the theoretical biochemical pathways, the amount of ATP synthesized in the steady state exceeds delta approximately P during contraction by more than twofold, corresponding to an apparent ADP:O ratio of 1.5. If it is assumed that carbohydrate oxidation is the only net chemical reaction in the steady state, the total heat production can be explained on the basis of the measured JO2. Under this assumption, heat production during recovery was less than that expected on the basis of the oxygen consumption and delta approximately P during contraction. These observations support the hypothesis that the unexplained enthalpy production and low apparent ADP:O ratio are causally related, i.e., that the reaction(s) producing the unexplained heat during contraction is reversed during the recovery period. PMID:6601686

Correlated patterns in hydrothermal plume distribution and apparent magmatic budget along 2500 km of the Southeast Indian Ridge

NASA Astrophysics Data System (ADS)

Baker, Edward T.; Hémond, Christophe; Briais, Anne; Maia, Marcia; Scheirer, Daniel S.; Walker, Sharon L.; Wang, Tingting; Chen, Yongshun John

2014-08-01

Multiple geological processes affect the distribution of hydrothermal venting along a mid-ocean ridge. Deciphering the role of a specific process is often frustrated by simultaneous changes in other influences. Here we take advantage of the almost constant spreading rate (65-71 mm/yr) along 2500 km of the Southeast Indian Ridge (SEIR) between 77°E and 99°E to examine the spatial density of hydrothermal venting relative to regional and segment-scale changes in the apparent magmatic budget. We use 227 vertical profiles of light backscatter and (on 41 profiles) oxidation-reduction potential along 27 first and second-order ridge segments on and adjacent to the Amsterdam-St. Paul (ASP) Plateau to map ph, the fraction of casts detecting a plume. At the regional scale, venting on the five segments crossing the magma-thickened hot spot plateau is almost entirely suppressed (ph = 0.02). Conversely, the combined ph (0.34) from all other segments follows the global trend of ph versus spreading rate. Off the ASP Plateau, multisegment trends in ph track trends in the regional axial depth, high where regional depth increases and low where it decreases. At the individual segment scale, a robust correlation between ph and cross-axis inflation for first-order segments shows that different magmatic budgets among first-order segments are expressed as different levels of hydrothermal spatial density. This correlation is absent among second-order segments. Eighty-five percent of the plumes occur in eight clusters totaling ˜350 km. We hypothesize that these clusters are a minimum estimate of the length of axial melt lenses underlying this section of the SEIR.

Electron-ion dissociative recombination rate constants relevant to the Titan atmosphere and the Interstellar Medium

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

Osborne, David; Lawson, Patrick; Adams, Nigel, E-mail: ngadams@uga.edu

Following the arrival of Cassini at Titan in 2004, the Titan atmosphere has been shown to contain large complex polycyclic-aromatic hydrocarbons. Since Cassini has provided a great deal of data, there exists a need for kinetic rate data to help with modeling this atmosphere. One type of kinetic data needed is electron-ion dissociative recombination (e-IDR) rate constants. These data are not readily available for larger compounds, such as naphthalene, or oxygen containing compounds, such as 1,4 dioxane or furan. Here, the rate constants for naphthalene, 1,4 dioxane, and furan have been measured and their temperature dependencies are determined when possible,more » using the University of Georgia's Variable Temperature Flowing Afterglow. The rate constants are compared with those previously published for other compounds; these show trends which illustrate the effects which multi-rings and oxygen heteroatoms substitutions have upon e-IDR rate constants.« less

Electron-ion dissociative recombination rate constants relevant to the Titan atmosphere and the Interstellar Medium

NASA Astrophysics Data System (ADS)

Osborne, David; Lawson, Patrick; Adams, Nigel

2014-01-01

Following the arrival of Cassini at Titan in 2004, the Titan atmosphere has been shown to contain large complex polycyclic-aromatic hydrocarbons. Since Cassini has provided a great deal of data, there exists a need for kinetic rate data to help with modeling this atmosphere. One type of kinetic data needed is electron-ion dissociative recombination (e-IDR) rate constants. These data are not readily available for larger compounds, such as naphthalene, or oxygen containing compounds, such as 1,4 dioxane or furan. Here, the rate constants for naphthalene, 1,4 dioxane, and furan have been measured and their temperature dependencies are determined when possible, using the University of Georgia's Variable Temperature Flowing Afterglow. The rate constants are compared with those previously published for other compounds; these show trends which illustrate the effects which multi-rings and oxygen heteroatoms substitutions have upon e-IDR rate constants.

Well hydraulics in pumping tests with exponentially decayed rates of abstraction in confined aquifers

NASA Astrophysics Data System (ADS)

Wen, Zhang; Zhan, Hongbin; Wang, Quanrong; Liang, Xing; Ma, Teng; Chen, Chen

2017-05-01

Actual field pumping tests often involve variable pumping rates which cannot be handled by the classical constant-rate or constant-head test models, and often require a convolution process to interpret the test data. In this study, we proposed a semi-analytical model considering an exponentially decreasing pumping rate started at a certain (higher) rate and eventually stabilized at a certain (lower) rate for cases with or without wellbore storage. A striking new feature of the pumping test with an exponentially decayed rate is that the drawdowns will decrease over a certain period of time during intermediate pumping stage, which has never been seen before in constant-rate or constant-head pumping tests. It was found that the drawdown-time curve associated with an exponentially decayed pumping rate function was bounded by two asymptotic curves of the constant-rate tests with rates equaling to the starting and stabilizing rates, respectively. The wellbore storage must be considered for a pumping test without an observation well (single-well test). Based on such characteristics of the time-drawdown curve, we developed a new method to estimate the aquifer parameters by using the genetic algorithm.

Impact of uncertainties in inorganic chemical rate constants on tropospheric composition and ozone radiative forcing

NASA Astrophysics Data System (ADS)

Newsome, Ben; Evans, Mat

2017-12-01

Chemical rate constants determine the composition of the atmosphere and how this composition has changed over time. They are central to our understanding of climate change and air quality degradation. Atmospheric chemistry models, whether online or offline, box, regional or global, use these rate constants. Expert panels evaluate laboratory measurements, making recommendations for the rate constants that should be used. This results in very similar or identical rate constants being used by all models. The inherent uncertainties in these recommendations are, in general, therefore ignored. We explore the impact of these uncertainties on the composition of the troposphere using the GEOS-Chem chemistry transport model. Based on the Jet Propulsion Laboratory (JPL) and International Union of Pure and Applied Chemistry (IUPAC) evaluations we assess the influence of 50 mainly inorganic rate constants and 10 photolysis rates on tropospheric composition through the use of the GEOS-Chem chemistry transport model. We assess the impact on four standard metrics: annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime. Uncertainty in the rate constants for NO2 + OH →M HNO3 and O3 + NO → NO2 + O2 are the two largest sources of uncertainty in these metrics. The absolute magnitude of the change in the metrics is similar if rate constants are increased or decreased by their σ values. We investigate two methods of assessing these uncertainties, addition in quadrature and a Monte Carlo approach, and conclude they give similar outcomes. Combining the uncertainties across the 60 reactions gives overall uncertainties on the annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime of 10, 11, 16 and 16 %, respectively. These are larger than the spread between models in recent model intercomparisons. Remote regions such as the tropics, poles and upper troposphere are most uncertain. This chemical uncertainty is sufficiently large to suggest that rate constant uncertainty should be considered alongside other processes when model results disagree with measurement. Calculations for the pre-industrial simulation allow a tropospheric ozone radiative forcing to be calculated of 0.412 ± 0.062 W m-2. This uncertainty (13 %) is comparable to the inter-model spread in ozone radiative forcing found in previous model-model intercomparison studies where the rate constants used in the models are all identical or very similar. Thus, the uncertainty of tropospheric ozone radiative forcing should expanded to include this additional source of uncertainty. These rate constant uncertainties are significant and suggest that refinement of supposedly well-known chemical rate constants should be considered alongside other improvements to enhance our understanding of atmospheric processes.

Effects of atmospheric composition on apparent activation energy of silicate weathering: I. Model formulation

NASA Astrophysics Data System (ADS)

Kanzaki, Yoshiki; Murakami, Takashi

2018-07-01

We have developed a weathering model to comprehensively understand the determining factors of the apparent activation energy of silicate weathering in order to better estimate the silicate-weathering flux in the Precambrian. The model formulates the reaction rate of a mineral as a basis, then the elemental loss by summing the reaction rates of whole minerals, and finally the weathering flux from a given weathering profile by integrating the elemental losses along the depth of the profile. The rate expressions are formulated with physicochemical parameters relevant to weathering, including solution and atmospheric compositions. The apparent activation energies of silicate weathering are then represented by the temperature dependences of the physicochemical parameters based on the rate expressions. It was found that the interactions between individual mineral-reactions and the compositions of solution and atmosphere are necessarily accompanied by those of temperature-dependence counterparts. Indeed, the model calculates the apparent activation energy of silicate weathering as a function of the temperature dependence of atmospheric CO2 (Δ HCO2‧) . The dependence of the apparent activation energy of silicate weathering on Δ HCO2‧ may explain the empirical dependence of silicate weathering on the atmospheric composition. We further introduce a compensation law between the apparent activation energy and the pre-exponential factor to obtain the relationship between the silicate-weathering flux (FCO2), temperature and the apparent activation energy. The model calculation and the compensation law enable us to predict FCO2 as a function of temperature, once Δ HCO2‧ is given. The validity of the model is supported by agreements between the model prediction and observations of the apparent activation energy and FCO2 in the modern weathering systems. The present weathering model will be useful for the estimation of FCO2 in the Precambrian, for which Δ HCO2‧ can be deduced from the greenhouse effect of atmospheric CO2.

Application of an Artificial Neural Network to the Prediction of OH Radical Reaction Rate Constants for Evaluating Global Warming Potential.

PubMed

Allison, Thomas C

2016-03-03

Rate constants for reactions of chemical compounds with hydroxyl radical are a key quantity used in evaluating the global warming potential of a substance. Experimental determination of these rate constants is essential, but it can also be difficult and time-consuming to produce. High-level quantum chemistry predictions of the rate constant can suffer from the same issues. Therefore, it is valuable to devise estimation schemes that can give reasonable results on a variety of chemical compounds. In this article, the construction and training of an artificial neural network (ANN) for the prediction of rate constants at 298 K for reactions of hydroxyl radical with a diverse set of molecules is described. Input to the ANN consists of counts of the chemical bonds and bends present in the target molecule. The ANN is trained using 792 (•)OH reaction rate constants taken from the NIST Chemical Kinetics Database. The mean unsigned percent error (MUPE) for the training set is 12%, and the MUPE of the testing set is 51%. It is shown that the present methodology yields rate constants of reasonable accuracy for a diverse set of inputs. The results are compared to high-quality literature values and to another estimation scheme. This ANN methodology is expected to be of use in a wide range of applications for which (•)OH reaction rate constants are required. The model uses only information that can be gathered from a 2D representation of the molecule, making the present approach particularly appealing, especially for screening applications.

A Computational Framework for Analyzing Stochasticity in Gene Expression

PubMed Central

Sherman, Marc S.; Cohen, Barak A.

2014-01-01

Stochastic fluctuations in gene expression give rise to distributions of protein levels across cell populations. Despite a mounting number of theoretical models explaining stochasticity in protein expression, we lack a robust, efficient, assumption-free approach for inferring the molecular mechanisms that underlie the shape of protein distributions. Here we propose a method for inferring sets of biochemical rate constants that govern chromatin modification, transcription, translation, and RNA and protein degradation from stochasticity in protein expression. We asked whether the rates of these underlying processes can be estimated accurately from protein expression distributions, in the absence of any limiting assumptions. To do this, we (1) derived analytical solutions for the first four moments of the protein distribution, (2) found that these four moments completely capture the shape of protein distributions, and (3) developed an efficient algorithm for inferring gene expression rate constants from the moments of protein distributions. Using this algorithm we find that most protein distributions are consistent with a large number of different biochemical rate constant sets. Despite this degeneracy, the solution space of rate constants almost always informs on underlying mechanism. For example, we distinguish between regimes where transcriptional bursting occurs from regimes reflecting constitutive transcript production. Our method agrees with the current standard approach, and in the restrictive regime where the standard method operates, also identifies rate constants not previously obtainable. Even without making any assumptions we obtain estimates of individual biochemical rate constants, or meaningful ratios of rate constants, in 91% of tested cases. In some cases our method identified all of the underlying rate constants. The framework developed here will be a powerful tool for deducing the contributions of particular molecular mechanisms to specific patterns of gene expression. PMID:24811315

Class Projects in Physical Organic Chemistry: The Hydrolysis of Aspirin

ERIC Educational Resources Information Center

Marrs, Peter S.

2004-01-01

An exercise that provides a hands-on demonstration of the hydrolysis of aspirin is presented. The key to understanding the hydrolysis is recognizing that all six process may occur simultaneously and that the observed rate constant is the sum of the rate constants that one rate constant dominates the overall process.

Effects of benzocaine on the kinetics of normal and batrachotoxin-modified Na channels in frog node of Ranvier.

PubMed Central

Schneider, M F; Dubois, J M

1986-01-01

The effects of benzocaine (0.5-1 mM) on normal Na currents, and on Na current and gating charge movement (Q) of batrachotoxin (BTX)-modified Na channels were analyzed in voltage-clamped frog node of Ranvier. Without BTX treatment the decay of Na current during pulses to between -40 and 0 mV could be decomposed into two exponential components both in the absence and in the presence of benzocaine. Benzocaine did not significantly alter the inactivation time constant of either component, but reduced both their amplitudes. The amplitude of the slow inactivating component was more decreased by benzocaine than the amplitude of the fast one, leading to an apparently faster decline of the overall Na current. After removal of Na inactivation and charge movement immobilization by BTX, benzocaine decreased the amplitude of INa with no change in time course. INa, QON, and QOFF were all reduced by the same factor. The results suggest that the rate of reaction of benzocaine with its receptor is slow compared to the rates of channel activation and inactivation. The differential effects of benzocaine on the two components of Na current inactivation in normal channels can be explained assuming two types of channel with different rates of inactivation and different affinities for the drug. PMID:2428413

Fenton Oxidation Kinetics and Intermediates of Nonylphenol Ethoxylates

PubMed Central

Cui, Kai; Yi, Hao; Zhou, Zi-jian; Zhuo, Qiong-fang; Bing, Yong-xin; Guo, Qing-wei; Xu, Zhen-cheng

2014-01-01

Abstract Removal of nonylphenol ethoxylates (NPEOs) in aqueous solution by Fenton oxidation process was studied in a laboratory-scale batch reactor. Operating parameters, including initial pH temperature, hydrogen peroxide, and ferrous ion dosage, were thoroughly investigated. Maximum NPEOs reduction of 84% was achieved within 6 min, under an initial pH of 3.0, 25°C, an H2O2 dosage of 9.74×10−3 M, and a molar ratio of [H2O2]/[Fe2+] of 3. A modified pseudo-first-order kinetic model was found to well represent experimental results. Correlations of reaction rate constants and operational parameters were established based on experimental data. Results indicated that the Fenton oxidation rate and removal efficiency were more dependent on the dosage of H2O2 than Fe2+, and the apparent activation energy (ΔE) was 17.5 kJ/mol. High-performance liquid chromatography and gas chromatograph mass spectrometer analytical results indicated degradation of NPEOs obtained within the first 2 min stepwise occurred by ethoxyl (EO) unit shortening. Long-chain NPEOs mixture demonstrated a higher degradation rate than shorter-chain ones. Nonylphenol (NP), short-chain NPEOs, and NP carboxyethoxylates were identified as the primary intermediates, which were mostly further degraded. PMID:24868141

Quantum calculations of the rate constant for the O(3P)+HCl reaction on new ab initio 3A″ and 3A' surfaces

NASA Astrophysics Data System (ADS)

Xie, Tiao; Bowman, Joel M.; Peterson, K. A.; Ramachandran, B.

2003-11-01

We report the thermal rate constant of the O(3P)+HCl→OH+Cl reaction calculated from 200 to 3200 K, using new fits to extensive ab initio calculations [B. Ramachandran and K. A. Peterson, J. Chem. Phys. 119, 9590 (2003), preceding paper]. The rate constants are obtained for both the 3A″ and 3A' surfaces using exact quantum reactive scattering calculations for selected values of the total angular momentum and the J-shifting approximation for both the 3A″ and 3A' surfaces. The results are compared with the ICVT/μOMT rate constants calculated by the POLYRATE program and all available experimental data. Other related high-energy reaction channels are also studied qualitatively for their contribution to the total thermal rate constant at high temperature.

Inflation with a constant rate of roll

NASA Astrophysics Data System (ADS)

Motohashi, Hayato; Starobinsky, Alexei A.; Yokoyama, Jun'ichi

2015-09-01

We consider an inflationary scenario where the rate of inflaton roll defined by ̈phi/H dot phi remains constant. The rate of roll is small for slow-roll inflation, while a generic rate of roll leads to the interesting case of 'constant-roll' inflation. We find a general exact solution for the inflaton potential required for such inflaton behaviour. In this model, due to non-slow evolution of background, the would-be decaying mode of linear scalar (curvature) perturbations may not be neglected. It can even grow for some values of the model parameter, while the other mode always remains constant. However, this always occurs for unstable solutions which are not attractors for the given potential. The most interesting particular cases of constant-roll inflation remaining viable with the most recent observational data are quadratic hilltop inflation (with cutoff) and natural inflation (with an additional negative cosmological constant). In these cases even-order slow-roll parameters approach non-negligible constants while the odd ones are asymptotically vanishing in the quasi-de Sitter regime.

On the ambiguity of the reaction rate constants in multivariate curve resolution for reversible first-order reaction systems.

PubMed

Schröder, Henning; Sawall, Mathias; Kubis, Christoph; Selent, Detlef; Hess, Dieter; Franke, Robert; Börner, Armin; Neymeyr, Klaus

2016-07-13

If for a chemical reaction with a known reaction mechanism the concentration profiles are accessible only for certain species, e.g. only for the main product, then often the reaction rate constants cannot uniquely be determined from the concentration data. This is a well-known fact which includes the so-called slow-fast ambiguity. This work combines the question of unique or non-unique reaction rate constants with factor analytic methods of chemometrics. The idea is to reduce the rotational ambiguity of pure component factorizations by considering only those concentration factors which are possible solutions of the kinetic equations for a properly adapted set of reaction rate constants. The resulting set of reaction rate constants corresponds to those solutions of the rate equations which appear as feasible factors in a pure component factorization. The new analysis of the ambiguity of reaction rate constants extends recent research activities on the Area of Feasible Solutions (AFS). The consistency with a given chemical reaction scheme is shown to be a valuable tool in order to reduce the AFS. The new methods are applied to model and experimental data. Copyright © 2016 Elsevier B.V. All rights reserved.

Temperature-Dependent Rate Constants and Substituent Effects for the Reactions of Hydroxyl Radicals With Three Partially Fluorinated Ethers

NASA Technical Reports Server (NTRS)

Hsu, K.-J.; DeMore, W. B.

1995-01-01

Rate constants and temperature dependencies for the reactions of OH with CF3OCH3 (HFOC-143a), CF2HOCF2H (HFOC-134), and CF3OCF2H (HFOC-125) were studied using a relative rate technique in the temperature range 298-393 K. The following absolute rate constants were derived: HFOC-143a, 1.9E-12 exp(-1555/T); HFOC-134, 1.9E-12 exp(-2006/T); HFOC-125, 4.7E-13 exp(-2095/T). Units are cm(exp 3)molecule(exp -1) s(exp -1). Substituent effects on OH abstraction rate constants are discussed, and it is shown that the CF3O group has an effect on the OH rate constants similar to that of a fluorine atom. The effects are related to changes in the C-H bond energies of the reactants (and thereby the activation energies) rather than changes in the preexponential factors. On the basis of a correlation of rate constants with bond energies, the respective D(C-H) bond strengths in the three ethers are found to be 102, 104, and 106 kcal/mol, with an uncertainty of about 1 kcal/mol.

Reaction of SO2 with OH in the atmosphere.

PubMed

Long, Bo; Bao, Junwei Lucas; Truhlar, Donald G

2017-03-15

The OH + SO 2 reaction plays a critical role in understanding the oxidation of SO 2 in the atmosphere, and its rate constant is critical for clarifying the fate of SO 2 in the atmosphere. The rate constant of the OH + SO 2 reaction is calculated here by using beyond-CCSDT correlation energy calculations for a benchmark, validated density functional methods for direct dynamics, canonical variational transition state theory with anharmonicity and multidimensional tunneling for the high-pressure rate constant, and system-specific quantum RRK theory for pressure effects; the combination of these methods can compete in accuracy with experiments. There has been a long-term debate in the literature about whether the OH + SO 2 reaction is barrierless, but our calculations indicate a positive barrier with an transition structure that has an enthalpy of activation of 0.27 kcal mol -1 at 0 K. Our results show that the high-pressure limiting rate constant of the OH + SO 2 reaction has a positive temperature dependence, but the rate constant at low pressures has a negative temperature dependence. The computed high-pressure limiting rate constant at 298 K is 1.25 × 10 -12 cm 3 molecule -1 s -1 , which agrees excellently with the value (1.3 × 10 -12 cm 3 molecule -1 s -1 ) recommended in the most recent comprehensive evaluation for atmospheric chemistry. We show that the atmospheric lifetime of SO 2 with respect to oxidation by OH depends strongly on altitude (in the range 0-50 km) due to the falloff effect. We introduce a new interpolation procedure for fitting the combined temperature and pressure dependence of the rate constant, and it fits the calculated rate constants over the whole range with a mean unsigned error of only 7%. The present results provide reliable kinetics data for this specific reaction, and also they demonstrate convenient theoretical methods that can be reliable for predicting rate constants of other gas-phase reactions.

An Excel tool for deriving key photosynthetic parameters from combined gas exchange and chlorophyll fluorescence: theory and practice.

PubMed

Bellasio, Chandra; Beerling, David J; Griffiths, Howard

2016-06-01

Combined photosynthetic gas exchange and modulated fluorometres are widely used to evaluate physiological characteristics associated with phenotypic and genotypic variation, whether in response to genetic manipulation or resource limitation in natural vegetation or crops. After describing relatively simple experimental procedures, we present the theoretical background to the derivation of photosynthetic parameters, and provide a freely available Excel-based fitting tool (EFT) that will be of use to specialists and non-specialists alike. We use data acquired in concurrent variable fluorescence-gas exchange experiments, where A/Ci and light-response curves have been measured under ambient and low oxygen. From these data, the EFT derives light respiration, initial PSII (photosystem II) photochemical yield, initial quantum yield for CO2 fixation, fraction of incident light harvested by PSII, initial quantum yield for electron transport, electron transport rate, rate of photorespiration, stomatal limitation, Rubisco (ribulose 1·5-bisphosphate carboxylase/oxygenase) rate of carboxylation and oxygenation, Rubisco specificity factor, mesophyll conductance to CO2 diffusion, light and CO2 compensation point, Rubisco apparent Michaelis-Menten constant, and Rubisco CO2 -saturated carboxylation rate. As an example, a complete analysis of gas exchange data on tobacco plants is provided. We also discuss potential measurement problems and pitfalls, and suggest how such empirical data could subsequently be used to parameterize predictive photosynthetic models. © 2015 John Wiley & Sons Ltd.

In Vitro Dissolution Tests of Plutonium and Americium Containing Contamination Originating From ZPPR Fuel Plates

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

William F. Bauer; Brian K. Schuetz; Gary M. Huestis

2012-09-01

Assessing the extent of internal dose is of concern whenever workers are exposed to airborne radionuclides or other contaminants. Internal dose determinations depend upon a reasonable estimate of the expected biological half-life of the contaminants in the respiratory tract. One issue with refractory elements is determining the dissolution rate of the element. Actinides such as plutonium (Pu) and Americium (Am) tend to be very refractory and can have biological half-lives of tens of years. In the event of an exposure, the dissolution rates of the radionuclides of interest needs to be assessed in order to assign the proper internal dosemore » estimates. During the November 2011 incident at the Idaho National Laboratory (INL) involving a ZPPR fuel plate, air filters in a constant air monitor (CAM) and a giraffe filter apparatus captured airborne particulate matter. These filters were used in dissolution rate experiments to determine the apparent dissolution half-life of Pu and Am in simulated biological fluids. This report describes these experiments and the results. The dissolution rates were found to follow a three term exponential decay equation. Differences were noted depending upon the nature of the biological fluid simulant. Overall, greater than 95% of the Pu and 93% of the Am were in a very slow dissolving component with dissolution half-lives of over 10 years.« less

Sampling frequency for water quality variables in streams: Systems analysis to quantify minimum monitoring rates.

PubMed

Chappell, Nick A; Jones, Timothy D; Tych, Wlodek

2017-10-15

Insufficient temporal monitoring of water quality in streams or engineered drains alters the apparent shape of storm chemographs, resulting in shifted model parameterisations and changed interpretations of solute sources that have produced episodes of poor water quality. This so-called 'aliasing' phenomenon is poorly recognised in water research. Using advances in in-situ sensor technology it is now possible to monitor sufficiently frequently to avoid the onset of aliasing. A systems modelling procedure is presented allowing objective identification of sampling rates needed to avoid aliasing within strongly rainfall-driven chemical dynamics. In this study aliasing of storm chemograph shapes was quantified by changes in the time constant parameter (TC) of transfer functions. As a proportion of the original TC, the onset of aliasing varied between watersheds, ranging from 3.9-7.7 to 54-79 %TC (or 110-160 to 300-600 min). However, a minimum monitoring rate could be identified for all datasets if the modelling results were presented in the form of a new statistic, ΔTC. For the eight H + , DOC and NO 3 -N datasets examined from a range of watershed settings, an empirically-derived threshold of 1.3(ΔTC) could be used to quantify minimum monitoring rates within sampling protocols to avoid artefacts in subsequent data analysis. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

College Student Disclosure of Non-Apparent Disabilities to Receive Classroom Accommodations

ERIC Educational Resources Information Center

Kranke, Derrick; Jackson, Sarah E.; Taylor, Debbie A.; Anderson-Fye, Eileen; Floersch, Jerry

2013-01-01

College students with psychiatric (non-apparent) disabilities have a much higher dropout rate and tend to underperform academically when compared with peers who do not have non-apparent disabilities. These students are also vulnerable because their disability could delay the development of milestones critical to adulthood. Limited research…

Rate constant for the fraction of atomic chlorine with formaldehyde from 200 to 500K

NASA Technical Reports Server (NTRS)

Michael, J. V.; Nava, D. F.; Payne, W. A.; Stief, L. J.

1978-01-01

A flash photolysis - resonance fluorescence technique was used to measure rate constant. The results were independent of substantial variations in H2CO, total pressure (Ar), and flash intensity (i.e., initial Cl). The rate constant was shown to be invariant with temperature, the best representation for this temperature range being K = (7.48 + or - 0.50) x 10 to the minus 11 power cu cm molecule-1 s-1 where the error is one standard deviation. The rate constant is theoretically discussed and the potential importance of the reaction in stratospheric chemistry is considered.

Impact of gas injection on the apparent viscosity and viscoelastic property of waste activated sewage sludge.

PubMed

Bobade, Veena; Baudez, Jean Christophe; Evans, Geoffery; Eshtiaghi, Nicky

2017-05-01

Gas injection is known to play a major role on the particle size of the sludge, the oxygen transfer rate, as well as the mixing efficiency of membrane bioreactors and aeration basins in the waste water treatment plants. The rheological characteristics of sludge are closely related to the particle size of the sludge floc. However, particle size of sludge floc depends partly on the shear induced in the sludge and partly on physico-chemical nature of the sludge. The objective of this work is to determine the impact of gas injection on both the apparent viscosity and viscoelastic property of sludge. The apparent viscosity of sludge was investigated by two methods: in-situ and after sparging. Viscosity curves obtained by in-situ measurement showed that the apparent viscosity decreases significantly from 4000 Pa s to 10 Pa s at low shear rate range (below 10 s -1 ) with an increase in gas flow rate (0.5LPM to 3LPM); however the after sparging flow curve analysis showed that the reduction in apparent viscosity throughout the shear rate range is negligible to be displayed. Torque and displacement data at low shear rate range revealed that the obtained lower apparent viscosity in the in-situ method is not the material characteristics, but the slippage effect due to a preferred location of the bubbles close to the bob, causing an inconsistent decrease of torque and increase of displacement at low shear rate range. In linear viscoelastic regime, the elastic and viscous modulus of sludge was reduced by 33% & 25%, respectively, due to gas injection because of induced shear. The amount of induced shear measured through two different tests (creep and time sweep) were the same. The impact of this induced shear on sludge structure was also verified by microscopic images. Copyright © 2017 Elsevier Ltd. All rights reserved.

Reaction kinetics of resveratrol with tert-butoxyl radicals

NASA Astrophysics Data System (ADS)

Džeba, Iva; Pedzinski, Tomasz; Mihaljević, Branka

2012-09-01

The rate constant for the reaction of t-butoxyl radicals with resveratrol was studied under pseudo-first order conditions. The rate constant was determined by measuring the phenoxyl radical formation rate at 390 nm as function of resveratrol concentration in acetonitrile. The rate constant was determined to be 6.5×108 M-1s-1. This high value indicates the high reactivity consistent with the strong antioxidant activity of resveratrol.

Kinetic Analysis for the Multistep Profiles of Organic Reactions: Significance of the Conformational Entropy on the Rate Constants of the Claisen Rearrangement.

PubMed

Sumiya, Yosuke; Nagahata, Yutaka; Komatsuzaki, Tamiki; Taketsugu, Tetsuya; Maeda, Satoshi

2015-12-03

The significance of kinetic analysis as a tool for understanding the reactivity and selectivity of organic reactions has recently been recognized. However, conventional simulation approaches that solve rate equations numerically are not amenable to multistep reaction profiles consisting of fast and slow elementary steps. Herein, we present an efficient and robust approach for evaluating the overall rate constants of multistep reactions via the recursive contraction of the rate equations to give the overall rate constants for the products and byproducts. This new method was applied to the Claisen rearrangement of allyl vinyl ether, as well as a substituted allyl vinyl ether. Notably, the profiles of these reactions contained 23 and 84 local minima, and 66 and 278 transition states, respectively. The overall rate constant for the Claisen rearrangement of allyl vinyl ether was consistent with the experimental value. The selectivity of the Claisen rearrangement reaction has also been assessed using a substituted allyl vinyl ether. The results of this study showed that the conformational entropy in these flexible chain molecules had a substantial impact on the overall rate constants. This new method could therefore be used to estimate the overall rate constants of various other organic reactions involving flexible molecules.

Climbing the Intercultural Ladder: The Gradual Adaptation Process to a Village Culture in Indonesia. Occasional Papers in Intercultural Learning #9.

ERIC Educational Resources Information Center

Hamke, Kerstin; Kievelitz, Uwe

Certain signs of culture shock apparently repeat themselves universally. Typical symptoms that indicate a reaction to new environments are: (1) feelings of constant exhaustion; (2) an increased necessity for sleep; (3) reduced activity and energy levels; and (4) headaches and diarrhea. These symptoms and other personal observations are chronicled…

Study on the dielectric properties of Al2O3/TiO2 sub-nanometric laminates: effect of the bottom electrode and the total thickness

NASA Astrophysics Data System (ADS)

Ben Elbahri, M.; Kahouli, A.; Mercey, B.; Lebedev, O.; Donner, W.; Lüders, U.

2018-02-01

Dielectrics based on amorphous sub-nanometric laminates of TiO2 and Al2O3 are subject to elevated dielectric losses and leakage currents, in large parts due to the extremely thin individual layer thickness chosen for the creation of the Maxwell-Wagner relaxation and therefore the high apparent dielectric constants. The optimization of performances of the laminate itself being strongly limited by this contradiction concerning its internal structure, we will show in this study that modifications of the dielectric stack of capacitors based on these sub-nanometric laminates can positively influence the dielectric losses and the leakage, as for example the nature of the electrodes, the introduction of thick insulating layers at the laminate/electrode interfaces and the modification of the total laminate thickness. The optimization of the dielectric stack leads to the demonstration of a capacitor with an apparent dielectric constant of 90, combined with low dielectric loss (tan δ) of 7 · 10-2 and with leakage currents smaller than 1  ×  10-6 A cm-2 at 10 MV m-1.

Monitoring, field experiments, and geochemical modeling of Fe(II) oxidation kinetics in a stream dominated by net-alkaline coal-mine drainage, Pennsylvania, USA

USGS Publications Warehouse

Cravotta, Charles A.

2015-01-01

Watershed-scale monitoring, field aeration experiments, and geochemical equilibrium and kinetic modeling were conducted to evaluate interdependent changes in pH, dissolved CO2, O2, and Fe(II) concentrations that typically take place downstream of net-alkaline, circumneutral coal-mine drainage (CMD) outfalls and during aerobic treatment of such CMD. The kinetic modeling approach, using PHREEQC, accurately simulates observed variations in pH, Fe(II) oxidation, alkalinity consumption, and associated dissolved gas concentrations during transport downstream of the CMD outfalls (natural attenuation) and during 6-h batch aeration tests on the CMD using bubble diffusers (enhanced attenuation). The batch aeration experiments demonstrated that aeration promoted CO2 outgassing, thereby increasing pH and the rate of Fe(II) oxidation. The rate of Fe(II) oxidation was accurately estimated by the abiotic homogeneous oxidation rate law −d[Fe(II)]/dt = k1·[O2]·[H+]−2·[Fe(II)] that indicates an increase in pH by 1 unit at pH 5–8 and at constant dissolved O2 (DO) concentration results in a 100-fold increase in the rate of Fe(II) oxidation. Adjusting for sample temperature, a narrow range of values for the apparent homogeneous Fe(II) oxidation rate constant (k1′) of 0.5–1.7 times the reference value of k1 = 3 × 10−12 mol/L/min (for pH 5–8 and 20 °C), reported by Stumm and Morgan (1996), was indicated by the calibrated models for the 5-km stream reach below the CMD outfalls and the aerated CMD. The rates of CO2 outgassing and O2ingassing in the model were estimated with first-order asymptotic functions, whereby the driving force is the gradient of the dissolved gas concentration relative to equilibrium with the ambient atmosphere. Although the progressive increase in DO concentration to saturation could be accurately modeled as a kinetic function for the conditions evaluated, the simulation of DO as an instantaneous equilibrium process did not affect the model results for Fe(II) or pH. In contrast, the model results for pH and Fe(II) were sensitive to the CO2 mass transfer rate constant (kL,CO2a). The value of kL,CO2a estimated for the stream (0.010 min−1) was within the range for the batch aeration experiments (0–0.033 min−1). These results indicate that the abiotic homogeneous Fe(II) oxidation rate law, with adjustments for variations in temperature and CO2 outgassing rate, may be applied to predict changes in aqueous iron and pH for net-alkaline, ferruginous waters within a stream (natural conditions) or a CMD treatment system (engineered conditions).

Studies on biomass char gasification and dynamics

NASA Astrophysics Data System (ADS)

You, Zhanping; You, Shijun; Ma, Xiaoyan

2018-01-01

The gasification performances of two kinds of biomass char by experiment methods are studied, including conversion rate and gasification gas component with temperature and time. Experimental results show that gasification temperature has important effects on the conversion rate and gas component. In the range of experimental temperature, char conversion rates are no more than 30.0%. The apparent activation energies and apparent reaction frequency factors of two biomass chars are obtained through kinetic studies.

A first-passage scheme for determination of overall rate constants for non-diffusion-limited suspensions

NASA Astrophysics Data System (ADS)

Lu, Shih-Yuan; Yen, Yi-Ming

2002-02-01

A first-passage scheme is devised to determine the overall rate constant of suspensions under the non-diffusion-limited condition. The original first-passage scheme developed for diffusion-limited processes is modified to account for the finite incorporation rate at the inclusion surface by using a concept of the nonzero survival probability of the diffusing entity at entity-inclusion encounters. This nonzero survival probability is obtained from solving a relevant boundary value problem. The new first-passage scheme is validated by an excellent agreement between overall rate constant results from the present development and from an accurate boundary collocation calculation for the three common spherical arrays [J. Chem. Phys. 109, 4985 (1998)], namely simple cubic, body-centered cubic, and face-centered cubic arrays, for a wide range of P and f. Here, P is a dimensionless quantity characterizing the relative rate of diffusion versus surface incorporation, and f is the volume fraction of the inclusion. The scheme is further applied to random spherical suspensions and to investigate the effect of inclusion coagulation on overall rate constants. It is found that randomness in inclusion arrangement tends to lower the overall rate constant for f up to the near close-packing value of the regular arrays because of the inclusion screening effect. This screening effect turns stronger for regular arrays when f is near and above the close-packing value of the regular arrays, and consequently the overall rate constant of the random array exceeds that of the regular array. Inclusion coagulation too induces the inclusion screening effect, and leads to lower overall rate constants.

Effects of tetraethylammonium on potassium currents in a molluscan neurons

PubMed Central

1981-01-01

The effects of tetraethylammonium (TEA) on the delayed K+ current and on the Ca2+-activated K+ current of the Aplysia pacemaker neurons R-15 and L-6 were studied. The delayed outward K+ current was measured in Ca2+-free ASW containing tetrodotoxin (TTX), using brief depolarizing clamp pulses. External TEA blocks the delayed K+ current reversibly in a dose-dependent manner. The experimental results are well fitted with a Michaelis-Menten expression, assuming a one-to-one reaction between TEA and a receptor site, with an apparent dissociation constant of 6.0 mM. The block depends on membrane voltage and is reduced at positive membrane potentials. The Ca2+-activated K+ current was measured in Ca2+- free artificial seawater (ASW) containing TTX, using internal Ca2+ ion injection to directly activate the K+ conductance. External TEA and a number of other quaternary ammonium ions block the Ca2+-activated K+ current reversibly in a dose-dependent manner. TEA is the most effective blocker, with an apparent dissociation constant, for a one-to- one reaction with a receptor site, of 0.4 mM. The block decreases with depolarization. The Ca2+-activated K+ current was also measured after intracellular iontophoretic TEA injection. Internal TEA blocks the Ca2+- activated K+ current (but the block is only apparent at positive membrane potentials), is increased by depolarization, and is irreversible. The effects of external and internal TEA can be seen in measurements of the total outward K+ current at different membrane potentials in normal ASW. PMID:6265594

On the compressible Taylor?Couette problem

NASA Astrophysics Data System (ADS)

Manela, A.; Frankel, I.

We consider the linear temporal stability of a Couette flow of a Maxwell gas within the gap between a rotating inner cylinder and a concentric stationary outer cylinder both maintained at the same temperature. The neutral curve is obtained for arbitrary Mach (Ma) and arbitrarily small Knudsen (Kn) numbers by use of a continuum model and is verified via comparison to direct simulation Monte Carlo results. At subsonic rotation speeds we find, for the radial ratios considered here, that the neutral curve nearly coincides with the constant-Reynolds-number curve pertaining to the critical value for the onset of instability in the corresponding incompressible-flow problem. With increasing Mach number, transition is deferred to larger Reynolds numbers. It is remarkable that for a fixed Reynolds number, instability is always eventually suppressed beyond some supersonic rotation speed. To clarify this we examine the variation with increasing (Ma) of the reference Couette flow and analyse the narrow-gap limit of the compressible TC problem. The results of these suggest that, as in the incompressible problem, the onset of instability at supersonic speeds is still essentially determined through the balance of inertial and viscous-dissipative effects. Suppression of instability is brought about by increased rates of dissipation associated with the elevated bulk-fluid temperatures occurring at supersonic speeds. A useful approximation is obtained for the neutral curve throughout the entire range of Mach numbers by an adaptation of the familiar incompressible stability criteria with the critical Reynolds (or Taylor) numbers now based on average fluid properties. The narrow-gap analysis further indicates that the resulting approximate neutral curve obtained in the (Ma, Kn) plane consists of two branches: (i) the subsonic part corresponding to a constant ratio (Ma/Kn) (i.e. a constant critical Reynolds number) and (ii) a supersonic branch which at large Ma values corresponds to a constant product Ma Kn. Finally, our analysis helps to resolve some conflicting views in the literature regarding apparently destabilizing compressibility effects.

Size, surface, and compositional tuning of the electronic and photocatalytic properties of II-VI quantum-size semiconductor nanocrystals

NASA Astrophysics Data System (ADS)

Korgel, Brian Allan

1997-11-01

Phosphatidylcholine vesicles provide reaction compartments for synthesis of size-quantized CdS nanocrystals of dimension predicted to within ±2 A based on initial encapsulated CdClsb2 concentration and vesicle diameter. Vesicle formation by detergent dialysis of phosphatidylcholine/hexylglucoside mixed micelles yields highly monodisperse lipid capsules within which monodisperse CdS nanoparticles are precipitated with sulfide. Size-quantized CdS nanocrystals, with diameters ranging from 20 to 60 A, have been produced with typical standard deviations about the mean diameter of ±8% as measured by transmission electron microscopy. By including ZnClsb2 or HgClsb2 in the dialyzate prior to vesicle formation, quantum-sized Znsb{y}Cdsb{1-y}S or Hgsb{y}Cdsb{1-y}S nanocrystal alloys with controlled stoichiometry are generated. Spectrophotometric and spectrofluorimetric measurements are consistent with highly crystalline, monodisperse particles with few core or surface defects. The alloyed nanocrystal spectra shift consistently with composition indicating a high degree of compositional control. Measured exciton energies for CdS show excellent agreement with data in the literature. The empirical pseudopotential model presented by Ramakrishna and Friesner for a cubic CdS lattice, correcting for experimentally measured lattice contractions, best fits the data. Size-quantized CdS nanocrystals serve as photocatalysts for nitrate reduction at neutral pH under conditions that mimic illumination by sunlight with overall product quantum yields of up to 4% for {˜}20 A, amine-terminated particles. Due to the effects of quantum confinement on electron and hole redox potentials, photocatalyzed nitrate reduction rates depend strongly on the particle size, and the fastest reduction rates are observed with the smallest nanocrystals. Using a Tafel plot and the empirical pseudopotential model to estimate electron redox potentials, the apparent electron transfer coefficient and the apparent standard rate constant is estimated at 0.23 and 4.0× 10sp{-12} cm/sec, respectively, for amine-terminated particles. Nitrate adsorption is important in this system and the effect on photoreduction rates is described well by a Langmuir-Hinschelwood expression. Nitrate reduction rates are reduced two-fold or more on negatively charged, carboxy-terminated nanocrystals that electrostatically repel nitrate. Reaction rates are additionally influenced by competetive chloride adsorption and surface charge modification due to solution pH.

Quantification aspects of constant pressure (ultra) high pressure liquid chromatography using mass-sensitive detectors with a nebulizing interface.

PubMed

Verstraeten, M; Broeckhoven, K; Lynen, F; Choikhet, K; Landt, K; Dittmann, M; Witt, K; Sandra, P; Desmet, G

2013-01-25

The present contribution investigates the quantitation aspects of mass-sensitive detectors with nebulizing interface (ESI-MSD, ELSD, CAD) in the constant pressure gradient elution mode. In this operation mode, the pressure is controlled and maintained at a set value and the liquid flow rate will vary according to the inverse mobile phase viscosity. As the pressure is continuously kept at the allowable maximum during the entire gradient run, the average liquid flow rate is higher compared to that in the conventional constant flow rate operation mode, thus shortening the analysis time. The following three mass-sensitive detectors were investigated: mass spectrometry detector (MS), evaporative light scattering detector (ELSD) and charged aerosol detector (CAD) and a wide variety of samples (phenones, polyaromatic hydrocarbons, wine, cocoa butter) has been considered. It was found that the nebulizing efficiency of the LC-interfaces of the three detectors under consideration changes with the increasing liquid flow rate. For the MS, the increasing flow rate leads to a lower peak area whereas for the ELSD the peak area increases compared to the constant flow rate mode. The peak area obtained with a CAD is rather insensitive to the liquid flow rate. The reproducibility of the peak area remains similar in both modes, although variation in system permeability compromises the 'long-term' reproducibility. This problem can however be overcome by running a flow rate program with an optimized flow rate and composition profile obtained from the constant pressure mode. In this case, the quantification remains reproducibile, despite any occuring variations of the system permeability. Furthermore, the same fragmentation pattern (MS) has been found in the constant pressure mode compared to the customary constant flow rate mode. Copyright © 2012 Elsevier B.V. All rights reserved.

Characteristic constants of 2,2',4'-trihydroxyazobenzene-5-sulfonic acid, a reagent for spectrophotometric analysis

USGS Publications Warehouse

Fletcher, Mary H.

1960-01-01

The dye 2,2',4'-trihydroxyazobenzene-5-sulfonic acid, has shown promise as a reagent for the determination of zirconium. As the literature contains very little information about this dye, basic data pertinent to its use as a reagent were determined. The sulfonic acid group and all three of the hydroxy groups show acidic characteristics. Apparent dissociation constants were determined for the three more labile protons and the approximate order of magnitude for the fourth constant was estimated. Absorption spectra for the different ionization species are given. A curve is also included which shows the fraction of dye in the different ionization forms at acidities from 10.35M hydrochloric acid to pH 11.9. A sixth dye species was found in 1.0 to 8.4M potassium hydroxide solutions, but its nature is unknown.

Bounding the Higgs boson width through interferometry.

PubMed

Dixon, Lance J; Li, Ye

2013-09-13

We study the change in the diphoton-invariant-mass distribution for Higgs boson decays to two photons, due to interference between the Higgs resonance in gluon fusion and the continuum background amplitude for gg→γγ. Previously, the apparent Higgs mass was found to shift by around 100 MeV in the standard model in the leading-order approximation, which may potentially be experimentally observable. We compute the next-to-leading-order QCD corrections to the apparent mass shift, which reduce it by about 40%. The apparent mass shift may provide a way to measure, or at least bound, the Higgs boson width at the Large Hadron Collider through "interferometry." We investigate how the shift depends on the Higgs width, in a model that maintains constant Higgs boson signal yields. At Higgs widths above 30 MeV, the mass shift is over 200 MeV and increases with the square root of the width. The apparent mass shift could be measured by comparing with the ZZ* channel, where the shift is much smaller. It might be possible to measure the shift more accurately by exploiting its strong dependence on the Higgs transverse momentum.

Cl(-) concentration dependence of photovoltage generation by halorhodopsin from Halobacterium salinarum.

PubMed Central

Muneyuki, Eiro; Shibazaki, Chie; Wada, Yoichiro; Yakushizin, Manabu; Ohtani, Hiroyuki

2002-01-01

The photovoltage generation by halorhodopsin from Halobacterium salinarum (shR) was examined by adsorbing shR-containing membranes onto a thin polymer film. The photovoltage consisted of two major components: one with a sub-millisecond range time constant and the other with a millisecond range time constant with different amplitudes, as previously reported. These components exhibited different Cl(-) concentration dependencies (0.1-9 M). We found that the time constant for the fast component was relatively independent of the Cl(-) concentration, whereas the time constant for the slow component increased sigmoidally at higher Cl(-) concentrations. The fast and the slow processes were attributed to charge (Cl(-)) movements within the protein and related to Cl(-) ejection, respectively. The laser photolysis studies of shR-membrane suspensions revealed that they corresponded to the formation and the decay of the N intermediate. The photovoltage amplitude of the slow component exhibited a distorted bell-shaped Cl(-) concentration dependence, and the Cl(-) concentration dependence of its time constant suggested a weak and highly cooperative Cl(-)-binding site(s) on the cytoplasmic side (apparent K(D) of approximately 5 M and Hill coefficient > or =5). The Cl(-) concentration dependence of the photovoltage amplitude and the time constant for the slow process suggested a competition between spontaneous relaxation and ion translocation. The time constant for the relaxation was estimated to be >100 ms. PMID:12324398

Kinetics of phloretin binding to phosphatidylcholine vesicle membranes

PubMed Central

1980-01-01

The submillisecond kinetics for phloretin binding to unilamellar phosphatidylcholine (PC) vesicles was investigated using the temperature-jump technique. Spectrophotometric studies of the equilibrium binding performed at 328 nm demonstrated that phloretin binds to a single set of independent, equivalent sites on the vesicle with a dissociation constant of 8.0 microM and a lipid/site ratio of 4.0. The temperature of the phloretin-vesicle solution was jumped by 4 degrees C within 4 microseconds producing a monoexponential, concentration-dependent relaxation process with time constants in the 30--200-microseconds time range. An analysis of the concentration dependence of relaxation time constants at pH 7.30 and 24 degrees C yielded a binding rate constant of 2.7 X 10(8) M-1 s-1 and an unbinding constant of 2,900 s-1; approximately 66 percent of total binding sites are exposed at the outer vesicle surface. The value of the binding rate constant and three additional observations suggest that the binding kinetics are diffusion limited. The phloretin analogue, naringenin, which has a diffusion coefficient similar to phloretin yet a dissociation constant equal to 24 microM, bound to PC vesicle with the same rate constant as phloretin did. In addition, the phloretin-PC system was studied in buffers made one to six times more viscous than water by addition of sucrose or glycerol to the differ. The equilibrium affinity for phloretin binding to PC vesicles is independent of viscosity, yet the binding rate constant decreases with the expected dependence (kappa binding alpha 1/viscosity) for diffusion-limited processes. Thus, the binding rate constant is not altered by differences in binding affinity, yet depends upon the diffusion coefficient in buffer. Finally, studies of the pH dependence of the binding rate constant showed a dependence (kappa binding alpha [1 + 10pH-pK]) consistent with the diffusion-limited binding of a weak acid. PMID:7391812

Evaluation of coupling terms between intra- and intermolecular vibrations in coarse-grained normal-mode analysis: does a stronger acid make a stiffer hydrogen bond?

PubMed

Houjou, Hirohiko

2011-10-21

Using theory of harmonic normal-mode vibration analysis, we developed a procedure for evaluating the anisotropic stiffness of intermolecular forces. Our scheme for coarse-graining of molecular motions is modified so as to account for intramolecular vibrations in addition to relative translational/rotational displacement. We applied this new analytical scheme to four carboxylic acid dimers, for which coupling between intra- and intermolecular vibrations is crucial for determining the apparent stiffness of the intermolecular double hydrogen bond. The apparent stiffness constant was analyzed on the basis of a conjunct spring model, which defines contributions from true intermolecular stiffness and molecular internal stiffness. Consequently, the true intermolecular stiffness was in the range of 43-48 N m(-1) for all carboxylic acids studied, regardless of the molecules' acidity. We concluded that the difference in the apparent stiffness can be attributed to differences in the internal stiffness of the respective molecules. © 2011 American Institute of Physics

Evaluation of coupling terms between intra- and intermolecular vibrations in coarse-grained normal-mode analysis: Does a stronger acid make a stiffer hydrogen bond?

NASA Astrophysics Data System (ADS)

Houjou, Hirohiko

2011-10-01

Using theory of harmonic normal-mode vibration analysis, we developed a procedure for evaluating the anisotropic stiffness of intermolecular forces. Our scheme for coarse-graining of molecular motions is modified so as to account for intramolecular vibrations in addition to relative translational/rotational displacement. We applied this new analytical scheme to four carboxylic acid dimers, for which coupling between intra- and intermolecular vibrations is crucial for determining the apparent stiffness of the intermolecular double hydrogen bond. The apparent stiffness constant was analyzed on the basis of a conjunct spring model, which defines contributions from true intermolecular stiffness and molecular internal stiffness. Consequently, the true intermolecular stiffness was in the range of 43-48 N m-1 for all carboxylic acids studied, regardless of the molecules' acidity. We concluded that the difference in the apparent stiffness can be attributed to differences in the internal stiffness of the respective molecules.

Temperature and pressure dependence of the absolute rate constant for the reactions of NH2 radicals with acetylene and ethylene

NASA Technical Reports Server (NTRS)

Bosco, S. R.; Nava, D. F.; Brobst, W. D.; Stief, L. J.

1984-01-01

The absolute rate constants for the reaction between the NH2 free radical and acetylene and ethylene is measured experimentally using a flash photolysis technique. The constant is considered to be a function of temperature and pressure. At each temperature level of the experiment, the observed pseudo-first-order rate constants were assumed to be independent of flash intensity. The results of the experiment indicate that the bimolecular rate constant for the NH2 + C2H2 reaction increases with pressure at 373 K and 459 K but not at lower temperatures. Results near the pressure limit conform to an Arrhenius expression of 1.11 (+ or -) 0.36 x 10 to the -13th over the temperature range from 241 to 459 K. For the reaction NH2 + C2H4, a smaller rate of increase in the bimolecular rate constant was observed over the temperature range 250-465 K. The implications of these results for current theoretical models of NH2 + C2H2 (or H4) reactions in the atmospheres of Jupiter and Saturn are discussed.

Determination of Bimolecular Rate Constants for Reactions of Hydroxyl Radical with Pharmaceutical and Cosmetics Chemicals - Implications to the Fate in the Aquatic Environment

NASA Astrophysics Data System (ADS)

Nakajima, H.; Arakaki, T.; Anastasio, C.

2008-12-01

Large organic compounds such as hyaluronic acid and chondroitin sulfate are often used in pharmaceutical and cosmetics products, but their chemical degradation pathways are not well understood. To better elucidate their fate in the aquatic environment, we initiated a study to determine bimolecular rate constants between these organic compounds and hydroxyl radical (OH), which is a potent oxidant in the environment. The lifetimes of many organic compounds are determined by reactions with OH radicals, and the lifetime of OH is often controlled by reactions with organic compounds. To determine these bimolecular rate constants we used a competition kinetics technique with either hydrogen peroxide or nitrate as a source of OH and benzoate as the competing sink. Since the molecular weights of some of the large organic compounds we studied were not known, we used dissolved organic carbon (DOC) concentrations to determine mole-carbon based bimolecular rate constants, instead of the commonly used molar-based bimolecular rate constants. We will report the mole-carbon based bimolecular rate constants of OH, determined at room temperature, with hyaluronic acid, chondroitin sulfate and some other large organic compounds.

Rheology of arc dacite lavas: experimental determination at low strain rates

NASA Astrophysics Data System (ADS)

Avard, Geoffroy; Whittington, Alan G.

2012-07-01

Andesitic-dacitic volcanoes exhibit a large variety of eruption styles, including explosive eruptions, endogenous and exogenous dome growth, and kilometer-long lava flows. The rheology of these lavas can be investigated through field observations of flow and dome morphology, but this approach integrates the properties of lava over a wide range of temperatures. Another approach is through laboratory experiments; however, previous studies have used higher shear stresses and strain rates than are appropriate to lava flows. We measured the apparent viscosity of several lavas from Santiaguito and Bezymianny volcanoes by uniaxial compression, between 1,109 and 1,315 K, at low shear stress (0.085 to 0.42 MPa), low strain rate (between 1.1 × 10-8 and 1.9 × 10-5 s-1), and up to 43.7 % total deformation. The results show a strong variability of the apparent viscosity between different samples, which can be ascribed to differences in initial porosity and crystallinity. Deformation occurs primarily by compaction, with some cracking and/or vesicle coalescence. Our experiments yield apparent viscosities more than 1 order of magnitude lower than predicted by models based on experiments at higher strain rates. At lava flow conditions, no evidence of a yield strength is observed, and the apparent viscosity is best approached by a strain rate- and temperature-dependent power law equation. The best fit for Santiaguito lava, for temperatures between 1,164 and 1,226 K and strain rates lower than 1.8 × 10-4 s-1, is log {η_{{app}}} = - 0.738 + 9.24 × {10^3}{/}T(K) - 0.654 \\cdot log dot{\\varepsilon } where η app is apparent viscosity and dot{\\varepsilon } is strain rate. This equation also reproduced 45 data for a sample from Bezymianny with a root mean square deviation of 0.19 log unit Pa s. Applying the rheological model to lava flow conditions at Santiaguito yields calculated apparent viscosities that are in reasonable agreement with field observations and suggests that internal shear heating may be significant ongoing heat source within these flows, enabling highly viscous lava to travel long distances.

Interaction of cinnamic acid derivatives with serum albumins: A fluorescence spectroscopic study

NASA Astrophysics Data System (ADS)

Singh, T. Sanjoy; Mitra, Sivaprasad

2011-03-01

Cinnamic acid (CA) derivatives are known to possess broad therapeutic applications including anti-tumor activity. The present study was designed to determine the underlying mechanism and thermodynamic parameters for the binding of two CA based intramolecular charge transfer (ICT) fluorescent probes, namely, 4-(dimethylamino) cinnamic acid (DMACA) and trans-ethyl p-(dimethylamino) cinnamate (EDAC), with albumins by fluorescence spectroscopy. Stern-Volmer analysis of the tryptophan fluorescence quenching data in presence of the added ligand reveals fluorescence quenching constant ( κq), Stern-Volmer constant ( KSV) and also the ligand-protein association constant ( Ka). The thermodynamic parameters like enthalpy (Δ H) and entropy (Δ S) change corresponding to the ligand binding process were also estimated. The results show that the ligands bind into the sub-domain IIA of the proteins in 1:1 stoichiometry with an apparent binding constant value in the range of 10 4 dm 3 mol -1. In both the cases, the spontaneous ligand binding to the proteins occur through entropy driven mechanism, although the interaction of DMACA is relatively stronger in comparison with EDAC. The temperature dependence of the binding constant indicates the induced change in protein secondary structure.

Calcium ion binding to a soil fulvic acid using a donnan potential model

USGS Publications Warehouse

Marinsky, J.A.; Mathuthu, A.; Ephraim, J.H.; Reddy, M.M.

1999-01-01

Calcium ion binding to a soil fulvic acid (Armadale Bh Horizon) was evaluated over a range of calcium ion concentrations, from pH 3.8 to 7.3, using potentiometric titrations and calcium ion electrode measurements. Fulvic acid concentration was constant (100 milligrams per liter) and calcium ion concentration varied up to 8 X 10-4 moles per liter. Experiments discussed here included: (1) titrations of fulvic acid-calcium ion containing solutions with sodium hydroxide; and (2) titrations of fully neutralized fulvic acid with calcium chloride solutions. Apparent binding constants (expressed as the logarithm of the value, log ??app) vary with solution pH, calcium ion concentration, degree of acid dissociation, and ionic strength (from log ??app = 2.5 to 3.9) and are similar to those reported by others. Fulvic acid charge, and the associated Donnan Potential, influences calcium ion-fulvic acid ion pair formation. A Donnan Potential corrrection term allowed calculation of intrinsic calcium ion-fulvic acid binding constants. Intrinsic binding constants vary from 1.2 to 2.5 (the average value is about log??= 1.6) and are similar to, but somewhat higher than, stability constants for calcium ion-carboxylic acid monodentate complexes. ?? by Oldenbourg Wissenschaftsverlag, Mu??nchen.

Temperature-independent energy expenditure in early development of the African clawed frog Xenopus laevis.

PubMed

Nagano, Yatsuhisa; Ode, Koji L

2014-08-01

The thermal dissipation of activated eggs and embryos undergoing development from cleavage to the tailbud stage of the African clawed frog Xenopus laevis was measured as a function of incubation time at temperatures ranging from T = 288.2 K to 295.2 K, using a high-precision isothermal calorimeter. A23187-mediated activation of mature eggs induced stable periodic thermal oscillations lasting for 8-34 h. The frequency agreed well with the cell cycle frequency of initial cleavages at the identical temperature. In the developing embryo, energy metabolism switches from embryonic to adult features during gastrulation. The thermal dissipation after gastrulation fit well with a single modified Avrami equation, which has been used for modeling crystal-growth. Both the oscillation frequency of the activated egg and the growth rate of the embryo strongly depend on temperature with the same apparent activation energy of approximately 87 kJ mole(-1). This result suggests that early development proceeds as a single biological time, attributable to a single metabolic rate. A temperature-independent growth curve was derived by scaling the thermogram to the biological time, indicating that the amount of energy expenditure during each developmental stage is constant over the optimal temperature range.

Bladder cancer mortality of workers exposed to aromatic amines: a 58-year follow-up.

PubMed

Pira, Enrico; Piolatto, Giorgio; Negri, Eva; Romano, Canzio; Boffetta, Paolo; Lipworth, Loren; McLaughlin, Joseph K; La Vecchia, Carlo

2010-07-21

We previously investigated bladder cancer risk in a cohort of dyestuff workers who were heavily exposed to aromatic amines from 1922 through 1972. We updated the follow-up by 14 years (through 2003) for 590 exposed workers to include more than 30 years of follow-up since last exposure to aromatic amines. Expected numbers of deaths from bladder cancer and other causes were computed by use of national mortality rates from 1951 to 1980 and regional mortality rates subsequently. There were 394 deaths, compared with 262.7 expected (standardized mortality ratio = 1.50, 95% confidence interval = 1.36 to 1.66). Overall, 56 deaths from bladder cancer were observed, compared with 3.4 expected (standardized mortality ratio = 16.5, 95% confidence interval = 12.4 to 21.4). The standardized mortality ratio for bladder cancer increased with younger age at first exposure and increasing duration of exposure. Although the standardized mortality ratio for bladder cancer steadily decreased with time since exposure stopped, the absolute risk remained approximately constant at 3.5 deaths per 1000 man-years up to 29 years after exposure stopped. Excess risk was apparent 30 years or more after last exposure.

Mathematical modeling of two phase stratified flow in a microchannel with curved interface

NASA Astrophysics Data System (ADS)

Dandekar, Rajat; Picardo, Jason R.; Pushpavanam, S.

2017-11-01

Stratified or layered two-phase flows are encountered in several applications of microchannels, such as solvent extraction. Assuming steady, unidirectional creeping flow, it is possible to solve the Stokes equations by the method of eigenfunctions, provided the interface is flat and meets the wall with a 90 degree contact angle. However, in reality the contact angle depends on the pair of liquids and the material of the channel, and differs significantly from 90 degrees in many practical cases. For unidirectional flow, this implies that the interface is a circular arc (of constant curvature). We solve this problem within the framework of eigenfunctions, using the procedure developed by Shankar. We consider two distinct cases: (a) the interface meets the wall with the equilibrium contact angle; (b) the interface is pinned by surface treatment of the walls, so that the flow rates determine the apparent contact angle. We show that the contact angle appreciably affects the velocity profile and the volume fractions of the liquids, while limiting the range of flow rates that can be sustained without the interface touching the top/bottom walls. Non-intuitively, we find that the pressure drop is reduced when the more viscous liquid wets the wall.

Factors influencing impingement of fish by Lake Ontario power plants

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

Wyman, R.L.; Dischel, R.S.

1984-01-01

Fish impinged by two Lake Ontario power plants were examined to determine the causal factors. Fish were near shore because they resided there, migrated there to spawn or forage, or because the water mass in which they resided moved near shore. Once near shore, fish abundance in impingement collections was correlated with demersal or pelagic behavior. Periodic increases in diversity and abundance of impinged fish corresponded with times of upwelling and thermocline oscillations. These data suggest that some species were segregated along temperature gradients and were impinged when the thermocline passed near the intake. Comparisons of impingement catch between twomore » power plants, one withdrawing a constant volume of water and the other a varying volume, showed that responses of fish to an intake were of three kinds. Alosa pseudoharengus and Osmerus mordax were apparently attracted to water currents entering the intake. Morone americana, Morone chrysops, Dorosoma cepedianum, and Perca flavescens were not influenced by changes in flow rate, suggesting that their impingement was proportional to their density in nearshore water. Micropterus dolomieui avoided the intake at higher flow rates in part due to rheotactic behavior. 25 references, 4 figures, 3 table.« less

The uncertainty of biodegradation rate constants of emerging organic compounds in soil and groundwater - A compilation of literature values for 82 substances.

PubMed

Greskowiak, Janek; Hamann, Enrico; Burke, Victoria; Massmann, Gudrun

2017-12-01

The present study reports on biodegradation rate constants of emerging organic compounds (EOCs) in soil and groundwater available in the literature. The major aim of this compilation was to provide an assessment of the uncertainty of hydrological models with respect to the fate of EOCs. The literature search identified a total number of 82 EOCs for which 1st-order rate constants could be derived. It was found that for the majority of compounds degradation rate constants vary over more than three orders of magnitude. Correlation to factors that are well known to affect the degradation rate, such as temperature or redox condition was weak. No correlation at all was found with results from available quantitative structure-activity relationship models. This suggests that many unknown site specific or experimentally specific factors influence the degradation behavior of EOCs in the environment. Thus, local and catchment scale predictive models to estimate EOC concentration at receptors, e.g., receiving waters or drinking water wells, need to consider the large uncertainty in 1st-order rate constants. As a consequence, applying rate constants that were derived from one experiment or field site investigation to other experiments or field sites should be done with extreme caution. Copyright © 2017 Elsevier Ltd. All rights reserved.

Assessment of rate of drug release from oil vehicle using a rotating dialysis cell.

PubMed

Larsen, D H; Fredholt, K; Larsen, C

2000-09-01

The rate constants for transfer of model compounds (naproxen and lidocaine) from oily vehicle (Viscoleo) to aqueous buffer phases were determined by use of the rotating dialysis cell. Release studies were done for the partly ionized compounds at several pH values. A correlation between the overall first-order rate constant related to attainment of equilibrium, k(obs), and the pH-dependent distribution coefficient, D, determined between oil vehicle and aqueous buffer was established according to the equation: logk(obs)=-0.71 logD-0.22 (k(obs) in h(-1)). Based on this correlation it was suggested that the rate constant of a weak electrolyte at a specified D value could be considered equal to the k(obs) value for a non-electrolyte possessing a partition coefficient, P(app), the magnitude of which was equal to D. Specific rate constants k(ow) and k(wo) were calculated from the overall rate constant and the pH-dependent distribution coefficient. The rate constant representing the transport from oily vehicle to aqueous phase, k(ow), was found to be significantly influenced by the magnitude of the partition coefficient P(app) according to: logk(ow)=-0.71 logP(app)-log(P(app)+1)-0.22 (k(ow) in h(-1)).