Reaction Order Ambiguity in Integrated Rate Plots

ERIC Educational Resources Information Center

Lee, Joe

2008-01-01

Integrated rate plots are frequently used in reaction kinetics to determine orders of reactions. It is often emphasised, when using this methodology in practice, that it is necessary to monitor the reaction to a substantial fraction of completion for these plots to yield unambiguous orders. The present article gives a theoretical and statistical…

PET kinetic analysis --pitfalls and a solution for the Logan plot.

PubMed

Kimura, Yuichi; Naganawa, Mika; Shidahara, Miho; Ikoma, Yoko; Watabe, Hiroshi

2007-01-01

The Logan plot is a widely used algorithm for the quantitative analysis of neuroreceptors using PET because it is easy to use and simple to implement. The Logan plot is also suitable for receptor imaging because its algorithm is fast. However, use of the Logan plot, and interpretation of the formed receptor images should be regarded with caution, because noise in PET data causes bias in the Logan plot estimates. In this paper, we describe the basic concept of the Logan plot in detail and introduce three algorithms for the Logan plot. By comparing these algorithms, we demonstrate the pitfalls of the Logan plot and discuss the solution.

Effect of vegetal cover on runoff and soil erosion under light intensity events. Rainfall simulation over USLE plots.

PubMed

Marques, María José; Bienes, Ramón; Jiménez, Luis; Pérez-Rodríguez, Raquel

2007-05-25

The erosive power of frequent light rainfalls is studied in this paper. Field experiments of simulated rainfall (Intensity, 21 mm h(-1) and kinetic energy, 13.5 J m(-2) mm(-1)) were conducted over 8 bounded USLE plots (80 m(2) each) with a slope of 10%. In 4 plots the soil was almost bare (<4% vegetation cover); the other 4 plots had almost full cover with natural vegetation in one year. Runoff and sediment yield was recorded. The results revealed the efficiency of vegetation cover reducing runoff and sediments. Runoff and sediments were negligible in covered plots. Therefore, in bare plots, although sediment yield was generally low, averaging 74+/-43 kg ha(-1), the mean of runoff achieved a coefficient of 35%, this magnitude has to be taken into consideration in this region verging on aridity. Rains around 13.5 J m(-2) mm(-1) of kinetic energy are quite frequent in the study area (34% of recorded rains en 12 years). If we would consider the usual lower limits from the literature, we would be ignoring an important percent of natural rainfall episodes.

Rate-dependent carbon and nitrogen kinetic isotope fractionation in hydrolysis of isoproturon.

PubMed

Penning, Holger; Cramer, Christopher J; Elsner, Martin

2008-11-01

Stable isotope fractionation permits quantifying contaminant degradation in the field when the transformation reaction is associated with a consistent isotope enrichment factor epsilon. When interpreted in conjunction with dual isotope plots, isotope fractionation is also particularly useful for elucidating reaction mechanisms. To assess the consistency of epsilon and dual isotope slopes in a two-step reaction, we investigated the abiotic hydrolysis of the herbicide isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea) using a fragmentation method that allows measuring isotope ratios in different parts of the molecule. Carbon and nitrogen position-specific isotope fractionation, as well as slopes in dual isotope plots, varied linearly with rate constants k(obs) depending on the presence of buffers that mediate the initial zwitterion formation. The correlation can be explained by two consecutive reaction steps (zwitterion formation followed by dimethylamine elimination) each of which has a different kinetic isotope effect and may be rate-limiting. Intrinsic isotope effects for both steps, extracted from our kinetic data using a novel theoretical treatment, agree well with values computed from density functional calculations. Our study therefore demonstrates that more variable isotope fractionation may be observed in simple chemical reactions than commonly thought, but that consistent epsilon or dual isotope slopes may nonetheless be encountered in certain molecular fragments.

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.

Noninvasive bi-graphical analysis for the quantification of slowly reversible radioligand binding

NASA Astrophysics Data System (ADS)

Seo, Seongho; Kim, Su Jin; Yoo, Hye Bin; Lee, Jee-Young; Kyeong Kim, Yu; Lee, Dong Soo; Zhou, Yun; Lee, Jae Sung

2016-09-01

In this paper, we presented a novel reference-region-based (noninvasive) bi-graphical analysis for the quantification of a reversible radiotracer binding that may be too slow to reach relative equilibrium (RE) state during positron emission tomography (PET) scans. The proposed method indirectly implements the noninvasive Logan plot, through arithmetic combination of the parameters of two other noninvasive methods and the apparent tissue-to-plasma efflux rate constant for the reference region (k2\\prime ). We investigated its validity and statistical properties, by performing a simulation study with various noise levels and k2\\prime values, and also evaluated its feasibility for [18F]FP-CIT PET in human brain. The results revealed that the proposed approach provides distribution volume ratio estimation comparable to the Logan plot at low noise levels while improving underestimation caused by non-RE state differently depending on k2\\prime . Furthermore, the proposed method was able to avoid noise-induced bias of the Logan plot, and the variability of its results was less dependent on k2\\prime than the Logan plot. Therefore, this approach, without issues related to arterial blood sampling given a pre-estimate of k2\\prime (e.g. population-based), could be useful in parametric image generation for slow kinetic tracers staying in a non-RE state within a PET scan.

Radioligand binding analysis of α 2 adrenoceptors with [11C]yohimbine in brain in vivo: Extended Inhibition Plot correction for plasma protein binding.

PubMed

Phan, Jenny-Ann; Landau, Anne M; Jakobsen, Steen; Wong, Dean F; Gjedde, Albert

2017-11-22

We describe a novel method of kinetic analysis of radioligand binding to neuroreceptors in brain in vivo, here applied to noradrenaline receptors in rat brain. The method uses positron emission tomography (PET) of [ 11 C]yohimbine binding in brain to quantify the density and affinity of α 2 adrenoceptors under condition of changing radioligand binding to plasma proteins. We obtained dynamic PET recordings from brain of Spraque Dawley rats at baseline, followed by pharmacological challenge with unlabeled yohimbine (0.3 mg/kg). The challenge with unlabeled ligand failed to diminish radioligand accumulation in brain tissue, due to the blocking of radioligand binding to plasma proteins that elevated the free fractions of the radioligand in plasma. We devised a method that graphically resolved the masking of unlabeled ligand binding by the increase of radioligand free fractions in plasma. The Extended Inhibition Plot introduced here yielded an estimate of the volume of distribution of non-displaceable ligand in brain tissue that increased with the increase of the free fraction of the radioligand in plasma. The resulting binding potentials of the radioligand declined by 50-60% in the presence of unlabeled ligand. The kinetic unmasking of inhibited binding reflected in the increase of the reference volume of distribution yielded estimates of receptor saturation consistent with the binding of unlabeled ligand.

Characterization of the efficiency of microbore liquid chromatography columns by van Deemter and kinetic plot analysis.

PubMed

Hetzel, Terence; Loeker, Denise; Teutenberg, Thorsten; Schmidt, Torsten C

2016-10-01

The efficiency of miniaturized liquid chromatography columns with inner diameters between 200 and 300 μm has been investigated using a dedicated micro-liquid chromatography system. Fully porous, core-shell and monolithic commercially available stationary phases were compared applying van Deemter and kinetic plot analysis. The sub-2 μm fully porous as well as the 2.7 μm core-shell particle packed columns showed superior efficiency and similar values for the minimum reduced plate heights (2.56-2.69) before correction for extra-column contribution compared to normal-bore columns. Moreover, the influence of extra-column contribution was investigated to demonstrate the difference between apparent and intrinsic efficiency by replacing the column by a zero dead volume union to determine the band spreading caused by the system. It was demonstrated that 72% of the intrinsic efficiency could be reached. The results of the kinetic plot analysis indicate the superior performance of the sub-2 μm fully porous particle packed column for ultra-fast liquid chromatography. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Degradation Kinetics Study of Alogliptin Benzoate in Alkaline Medium by Validated Stability-Indicating HPTLC Method.

PubMed

Bodiwala, Kunjan Bharatkumar; Shah, Shailesh; Thakor, Jeenal; Marolia, Bhavin; Prajapati, Pintu

2016-11-01

A rapid, sensitive, and stability-indicating high-performance thin-layer chromatographic method was developed and validated to study degradation kinetics of Alogliptin benzoate (ALG) in an alkaline medium. ALG was degraded under acidic, alkaline, oxidative, and thermal stress conditions. The degraded samples were chromatographed on silica gel 60F254-TLC plates, developed using a quaternary-solvent system (chloroform-methanol-ethyl acetate-triethyl amine, 9+1+1+0.5, v/v/v/v), and scanned at 278 nm. The developed method was validated per International Conference on Harmonization guidelines using validation parameters such as specificity, linearity and range, precision, accuracy, LOD, and LOQ. The linearity range for ALG was 100-500 ng/band (correlation coefficient = 0.9997) with an average recovery of 99.47%. The LOD and LOQ for ALG were 9.8 and 32.7 ng/band, respectively. The developed method was successfully applied for the quantitative estimation of ALG in its synthetic mixture with common excipients. Degradation kinetics of ALG in an alkaline medium was studied by degrading it under three different temperatures and three different concentrations of alkali. Degradation of ALG in the alkaline medium was found to follow first-order kinetics. Contour plots have been generated to predict degradation rate constant, half-life, and shelf life of ALG in various combinations of temperature and concentration of alkali using Design Expert software.

Kinetic efficiency of polar monolithic capillary columns in high-pressure gas chromatography.

PubMed

Kurganov, A A; Korolev, A A; Shiryaeva, V E; Popova, T P; Kanateva, A Yu

2013-11-08

Poppe plots were used for analysis of kinetic efficiency of monolithic sorbents synthesized in quartz capillaries for utilization in high-pressure gas chromatography. Values of theoretical plate time and maximum number of theoretical plates occurred to depend significantly on synthetic parameters such as relative amount of monomer in the initial polymerization mixture, temperature and polymerization time. Poppe plots let one to find synthesis conditions suitable either for high-speed separations or for maximal efficiency. It is shown that construction of kinetic Poppe curves using potential Van Deemter data demands compressibility of mobile phase to be taken into consideration in the case of gas chromatography. Model mixture of light hydrocarbons C1 to C4 was then used for investigation of influence of carrier gas nature on kinetic efficiency of polymeric monolithic columns. Minimal values of theoretical plate times were found for CO2 and N2O carrier gases. Copyright © 2013 Elsevier B.V. All rights reserved.

Heterogeneous Molecular Catalysis of Electrochemical Reactions: Volcano Plots and Catalytic Tafel Plots.

PubMed

Costentin, Cyrille; Savéant, Jean-Michel

2017-06-14

We analyze here, in the framework of heterogeneous molecular catalysis, the reasons for the occurrence or nonoccurrence of volcanoes upon plotting the kinetics of the catalytic reaction versus the stabilization free energy of the primary intermediate of the catalytic process. As in the case of homogeneous molecular catalysis or catalysis by surface-active metallic sites, a strong motivation of such studies relates to modern energy challenges, particularly those involving small molecules, such as water, hydrogen, oxygen, proton, and carbon dioxide. This motivation is particularly pertinent for what concerns heterogeneous molecular catalysis, since it is commonly preferred to homogeneous molecular catalysis by the same molecules if only for chemical separation purposes and electrolytic cell architecture. As with the two other catalysis modes, the main drawback of the volcano plot approach is the basic assumption that the kinetic responses depend on a single descriptor, viz., the stabilization free energy of the primary intermediate. More comprehensive approaches, investigating the responses to the maximal number of experimental factors, and conveniently expressed as catalytic Tafel plots, should clearly be preferred. This is more so in the case of heterogeneous molecular catalysis in that additional transport factors in the supporting film may additionally affect the current-potential responses. This is attested by the noteworthy presence of maxima in catalytic Tafel plots as well as their dependence upon the cyclic voltammetric scan rate.

Measuring kinetics of complex single ion channel data using mean-variance histograms.

PubMed

Patlak, J B

1993-07-01

The measurement of single ion channel kinetics is difficult when those channels exhibit subconductance events. When the kinetics are fast, and when the current magnitudes are small, as is the case for Na+, Ca2+, and some K+ channels, these difficulties can lead to serious errors in the estimation of channel kinetics. I present here a method, based on the construction and analysis of mean-variance histograms, that can overcome these problems. A mean-variance histogram is constructed by calculating the mean current and the current variance within a brief "window" (a set of N consecutive data samples) superimposed on the digitized raw channel data. Systematic movement of this window over the data produces large numbers of mean-variance pairs which can be assembled into a two-dimensional histogram. Defined current levels (open, closed, or sublevel) appear in such plots as low variance regions. The total number of events in such low variance regions is estimated by curve fitting and plotted as a function of window width. This function decreases with the same time constants as the original dwell time probability distribution for each of the regions. The method can therefore be used: 1) to present a qualitative summary of the single channel data from which the signal-to-noise ratio, open channel noise, steadiness of the baseline, and number of conductance levels can be quickly determined; 2) to quantify the dwell time distribution in each of the levels exhibited. In this paper I present the analysis of a Na+ channel recording that had a number of complexities. The signal-to-noise ratio was only about 8 for the main open state, open channel noise, and fast flickers to other states were present, as were a substantial number of subconductance states. "Standard" half-amplitude threshold analysis of these data produce open and closed time histograms that were well fitted by the sum of two exponentials, but with apparently erroneous time constants, whereas the mean-variance histogram technique provided a more credible analysis of the open, closed, and subconductance times for the patch. I also show that the method produces accurate results on simulated data in a wide variety of conditions, whereas the half-amplitude method, when applied to complex simulated data shows the same errors as were apparent in the real data. The utility and the limitations of this new method are discussed.

Thermal decomposition and kinetics of coal and fermented cornstalk using thermogravimetric analysis.

PubMed

He, Yuyuan; Chang, Chun; Li, Pan; Han, Xiuli; Li, Hongliang; Fang, Shuqi; Chen, Junying; Ma, Xiaojian

2018-07-01

The thermal behavior and kinetics of Yiluo coal (YC) and the residues of fermented cornstalk (FC) were investigated in this study. The Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO) methods were used for the kinetic analysis of the pyrolysis process. The results showed that the activation energy (E α ) was increased with the increase of the thermal conversion rate (α), and the average values of E α of YC, FC and the blend (m YC /m FC  = 6/4) were 304.26, 224.94 and 233.46 kJ/mol, respectively. The order reaction model function for the blend was also developed by the master-plots method. By comparing the E a and the enthalpy, it was found that the blend was favored to format activated complex due to the lower potential energy barrier. Meanwhile, the average value of Gibbs free energy of the blend was 169.83 kJ/mol, and the changes of entropies indicated that the pyrolysis process was evolved from ordered-state to disordered-state. Copyright © 2018 Elsevier Ltd. All rights reserved.

Discrete kinetic models from funneled energy landscape simulations.

PubMed

Schafer, Nicholas P; Hoffman, Ryan M B; Burger, Anat; Craig, Patricio O; Komives, Elizabeth A; Wolynes, Peter G

2012-01-01

A general method for facilitating the interpretation of computer simulations of protein folding with minimally frustrated energy landscapes is detailed and applied to a designed ankyrin repeat protein (4ANK). In the method, groups of residues are assigned to foldons and these foldons are used to map the conformational space of the protein onto a set of discrete macrobasins. The free energies of the individual macrobasins are then calculated, informing practical kinetic analysis. Two simple assumptions about the universality of the rate for downhill transitions between macrobasins and the natural local connectivity between macrobasins lead to a scheme for predicting overall folding and unfolding rates, generating chevron plots under varying thermodynamic conditions, and inferring dominant kinetic folding pathways. To illustrate the approach, free energies of macrobasins were calculated from biased simulations of a non-additive structure-based model using two structurally motivated foldon definitions at the full and half ankyrin repeat resolutions. The calculated chevrons have features consistent with those measured in stopped flow chemical denaturation experiments. The dominant inferred folding pathway has an "inside-out", nucleation-propagation like character.

Prediction of scuffing failure based on competitive kinetics of oxide formation and removal: Application to lubricated sliding of AISI 52100 steel on steel

NASA Astrophysics Data System (ADS)

Cutiongco, Eric C.; Chung, Yip-Wah

1994-07-01

A method for predicting scuffing failure based on the competitive kinetics of oxide formation and removal has been developed and applied to the sliding of AISI 52100 steel on steel with poly-alpha-olefin as the lubricant. Oxide formation rates were determining using static oxidation tests on coupons of 52100 steel covered with poly-alpha-olefin at temperatures of 140 C to 250 C. Oxide removal rates were determined at different combinations of initial average nominal contact pressures (950 MPa to 1578 MPa) and sliding velocities (0.4 m/s to 1.8 m/s) using a ball-on-disk vacuum tribotester. The nominal asperity flash temperatures generated during the wear tests were calculated and the temperatures corresponding to the intersection of the the Arrhenius plots of oxide formation and removal rates were determined and taken as the critical failure temperatures. The pressure-velocity failure transition diagram was constructed by plotting the critical failure temperatures along isotherms of average nominal asperity flash temperatures calculated at different combinations of contact stress and sliding speed. The predicted failure transition curve agreed well with experimental scuffing data.

Kinetics and mechanism of olefin catalytic hydroalumination by organoaluminum compounds

NASA Astrophysics Data System (ADS)

Koledina, K. F.; Gubaidullin, I. M.

2016-05-01

The complex reaction mechanism of α-olefin catalytic hydroalumination by alkylalanes is investigated via mathematical modeling that involves plotting the kinetic models for the individual reactions that make up a complex system and a separate study of their principles. Kinetic parameters of olefin catalytic hydroalumination are estimated. Activation energies of the possible steps of the schemes of complex reaction mechanisms are compared and possible reaction pathways are determined.

Supersymmetric quantum mechanics method for the Fokker-Planck equation with applications to protein folding dynamics

NASA Astrophysics Data System (ADS)

Polotto, Franciele; Drigo Filho, Elso; Chahine, Jorge; Oliveira, Ronaldo Junio de

2018-03-01

This work developed analytical methods to explore the kinetics of the time-dependent probability distributions over thermodynamic free energy profiles of protein folding and compared the results with simulation. The Fokker-Planck equation is mapped onto a Schrödinger-type equation due to the well-known solutions of the latter. Through a semi-analytical description, the supersymmetric quantum mechanics formalism is invoked and the time-dependent probability distributions are obtained with numerical calculations by using the variational method. A coarse-grained structure-based model of the two-state protein Tm CSP was simulated at a Cα level of resolution and the thermodynamics and kinetics were fully characterized. Analytical solutions from non-equilibrium conditions were obtained with the simulated double-well free energy potential and kinetic folding times were calculated. It was found that analytical folding time as a function of temperature agrees, quantitatively, with simulations and experiments from the literature of Tm CSP having the well-known 'U' shape of the Chevron Plots. The simple analytical model developed in this study has a potential to be used by theoreticians and experimentalists willing to explore, quantitatively, rates and the kinetic behavior of their system by informing the thermally activated barrier. The theory developed describes a stochastic process and, therefore, can be applied to a variety of biological as well as condensed-phase two-state systems.

Analyzing bean extracts using time-dependent SDS trapping to quantify the kinetic stability of phaseolin proteins.

PubMed

Thibeault, Jane; Church, Jennifer; Ortiz-Perez, Brian; Addo, Samuel; Hill, Shakeema; Khalil, Areeg; Young, Malaney; Xia, Ke; Colón, Wilfredo

2017-09-30

In common beans and lima bean, the storage protein phaseolin is difficult to degrade and SDS-resistant, a sign of kinetic stability. Kinetically stable proteins (KSPs) are characterized by having a high-energy barrier between the native and denatured states that results in very slow unfolding. Such proteins are resistant to proteolytic degradation and detergents, such as SDS. Here the method SDS-Trapping of Proteins (S-TraP) is applied directly on bean extracts to quantify the kinetic stability of phaseolin in lima bean and several common beans, including black bean, navy bean, and small red bean. The bean extracts were incubated in SDS at various temperatures (60-75 °C) for different time periods, followed by SDS-PAGE analysis at room temperature, and subsequent band quantification to determine the kinetics of phaseolin unfolding. Eyring plot analysis showed that the phaseolin from each bean has high kinetic stability, with an SDS-trapping (i.e. unfolding) half-life ranging from about 20-100 years at 24 °C and 2-7 years at 37 °C. The remarkably high kinetic stability of these phaseolin proteins is consistent with the low digestibility of common beans and lima bean, as well as their relatively high germination temperatures. From a practical perspective, this work exemplifies that S-TraP is a useful and cost-effective method for quantifying the kinetic stability of proteins in biological extracts or lysates. Depending on the protein to be studied and its abundance, S-TraP may be performed directly on the extract without need for protein purification. Copyright © 2017 Elsevier Inc. All rights reserved.

Kinetic study of the thermal decomposition of uranium metaphosphate, U(PO3)4, into uranium pyrophosphate, UP2O7

NASA Astrophysics Data System (ADS)

Yang, Hee-Chul; Kim, Hyung-Ju; Lee, Si-Young; Yang, In-Hwan; Chung, Dong-Yong

2017-06-01

The thermochemical properties of uranium compounds have attracted much interest in relation to thermochemical treatments and the safe disposal of radioactive waste bearing uranium compounds. The characteristics of the thermal decomposition of uranium metaphosphate, U(PO3)4, into uranium pyrophosphate, UP2O7, have been studied from the view point of reaction kinetics and acting mechanisms. A mixture of U(PO3)4 and UP2O7 was prepared from the pyrolysis residue of uranium-bearing spent TBP. A kinetic analysis of the reaction of U(PO3)4 into UP2O7 was conducted using an isoconversional method and a master plot method on the basis of data from a non-isothermal thermogravimetric analysis. The thermal decomposition of U(PO3)4 into UP2O7 followed a single-step reaction with an activation energy of 175.29 ± 1.58 kJ mol-1. The most probable kinetic model was determined as a type of nucleation and nuclei-growth models, the Avrami-Erofeev model (A3), which describes that there are certain restrictions on nuclei growth of UP2O7 during the solid-state decomposition of U(PO3)4.

Kinetics and mechanism of solid decompositions — From basic discoveries by atomic absorption spectrometry and quadrupole mass spectroscopy to thorough thermogravimetric analysis

NASA Astrophysics Data System (ADS)

L'vov, Boris V.

2008-02-01

This paper sums up the evolution of thermochemical approach to the interpretation of solid decompositions for the past 25 years. This period includes two stages related to decomposition studies by different techniques: by ET AAS and QMS in 1981-2001 and by TG in 2002-2007. As a result of ET AAS and QMS investigations, the method for determination of absolute rates of solid decompositions was developed and the mechanism of decompositions through the congruent dissociative vaporization was discovered. On this basis, in the period from 1997 to 2001, the decomposition mechanisms of several classes of reactants were interpreted and some unusual effects observed in TA were explained. However, the thermochemical approach has not received any support by other TA researchers. One of the potential reasons of this distrust was the unreliability of the E values measured by the traditional Arrhenius plot method. The theoretical analysis and comparison of metrological features of different methods used in the determinations of thermochemical quantities permitted to conclude that in comparison with the Arrhenius plot and second-law methods, the third-law method is to be very much preferred. However, this method cannot be used in the kinetic studies by the Arrhenius approach because its use suggests the measuring of the equilibrium pressures of decomposition products. On the contrary, the method of absolute rates is ideally suitable for this purpose. As a result of much higher precision of the third-law method, some quantitative conclusions that follow from the theory were confirmed, and several new effects, which were invisible in the framework of the Arrhenius approach, have been revealed. In spite of great progress reached in the development of reliable methodology, based on the third-law method, the thermochemical approach remains unclaimed as before.

A Graphical User Interface for a Method to Infer Kinetics and Network Architecture (MIKANA)

PubMed Central

Mourão, Márcio A.; Srividhya, Jeyaraman; McSharry, Patrick E.; Crampin, Edmund J.; Schnell, Santiago

2011-01-01

One of the main challenges in the biomedical sciences is the determination of reaction mechanisms that constitute a biochemical pathway. During the last decades, advances have been made in building complex diagrams showing the static interactions of proteins. The challenge for systems biologists is to build realistic models of the dynamical behavior of reactants, intermediates and products. For this purpose, several methods have been recently proposed to deduce the reaction mechanisms or to estimate the kinetic parameters of the elementary reactions that constitute the pathway. One such method is MIKANA: Method to Infer Kinetics And Network Architecture. MIKANA is a computational method to infer both reaction mechanisms and estimate the kinetic parameters of biochemical pathways from time course data. To make it available to the scientific community, we developed a Graphical User Interface (GUI) for MIKANA. Among other features, the GUI validates and processes an input time course data, displays the inferred reactions, generates the differential equations for the chemical species in the pathway and plots the prediction curves on top of the input time course data. We also added a new feature to MIKANA that allows the user to exclude a priori known reactions from the inferred mechanism. This addition improves the performance of the method. In this article, we illustrate the GUI for MIKANA with three examples: an irreversible Michaelis–Menten reaction mechanism; the interaction map of chemical species of the muscle glycolytic pathway; and the glycolytic pathway of Lactococcus lactis. We also describe the code and methods in sufficient detail to allow researchers to further develop the code or reproduce the experiments described. The code for MIKANA is open source, free for academic and non-academic use and is available for download (Information S1). PMID:22096591

A graphical user interface for a method to infer kinetics and network architecture (MIKANA).

PubMed

Mourão, Márcio A; Srividhya, Jeyaraman; McSharry, Patrick E; Crampin, Edmund J; Schnell, Santiago

2011-01-01

One of the main challenges in the biomedical sciences is the determination of reaction mechanisms that constitute a biochemical pathway. During the last decades, advances have been made in building complex diagrams showing the static interactions of proteins. The challenge for systems biologists is to build realistic models of the dynamical behavior of reactants, intermediates and products. For this purpose, several methods have been recently proposed to deduce the reaction mechanisms or to estimate the kinetic parameters of the elementary reactions that constitute the pathway. One such method is MIKANA: Method to Infer Kinetics And Network Architecture. MIKANA is a computational method to infer both reaction mechanisms and estimate the kinetic parameters of biochemical pathways from time course data. To make it available to the scientific community, we developed a Graphical User Interface (GUI) for MIKANA. Among other features, the GUI validates and processes an input time course data, displays the inferred reactions, generates the differential equations for the chemical species in the pathway and plots the prediction curves on top of the input time course data. We also added a new feature to MIKANA that allows the user to exclude a priori known reactions from the inferred mechanism. This addition improves the performance of the method. In this article, we illustrate the GUI for MIKANA with three examples: an irreversible Michaelis-Menten reaction mechanism; the interaction map of chemical species of the muscle glycolytic pathway; and the glycolytic pathway of Lactococcus lactis. We also describe the code and methods in sufficient detail to allow researchers to further develop the code or reproduce the experiments described. The code for MIKANA is open source, free for academic and non-academic use and is available for download (Information S1).

Pyrolysis reaction models of waste tires: Application of Master-Plots method for energy conversion via devolatilization.

PubMed

Irmak Aslan, Dilan; Parthasarathy, Prakash; Goldfarb, Jillian L; Ceylan, Selim

2017-10-01

Land applied disposal of waste tires has far-reaching environmental, economic, and human health consequences. Pyrolysis represents a potential waste management solution, whereby the solid carbonaceous residue is heated in the absence of oxygen to produce liquid and gaseous fuels, and a solid char. The design of an efficient conversion unit requires information on the reaction kinetics of pyrolysis. This work is the first to probe the appropriate reaction model of waste tire pyrolysis. The average activation energy of pyrolysis was determined via iso-conversional methods over a mass fraction conversion range between 0.20 and 0.80 to be 162.8±23.2kJmol -1 . Using the Master Plots method, a reaction order of three was found to be the most suitable model to describe the pyrolytic decomposition. This suggests that the chemical reactions themselves (cracking, depolymerization, etc.), not diffusion or boundary layer interactions common with carbonaceous biomasses, are the rate-limiting steps in the pyrolytic decomposition of waste tires. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comments on Static vs Kinetic Friction

NASA Astrophysics Data System (ADS)

Kessler, Gabriel

2009-09-01

I'm writing to comment on the article published in the March edition of The Physics Teacher titled "Choose Wisely: Static or Kinetic Friction—The Power of Dimensionless Plots." As I was reading the article, something caught my eye that I couldn't reconcile with. It was the phrase on page 160 in the first column near the bottom. The statement was that the experimental value for the coefficient of kinetic friction was "unexpectedly greater than the coefficient of static friction!"

Kinetics of lisinopril intramolecular cyclization in solid phase monitored by Fourier transform infrared microscopy.

PubMed

Widjaja, Effendi; Tan, Wei Jian

2008-08-01

The solid-state intramolecular cyclization of lisinopril to diketopiperazine was investigated by in situ Fourier transform infrared (FT-IR) microscopy. Using a controllable heating cell, the isothermal transformation was monitored in situ at 147.5, 150, 152.5, 155, and 157.5 degrees C. The collected time-dependent FT-IR spectra at each isothermal temperature were preprocessed and analyzed using a multivariate chemometric approach. The pure component spectra of the observable component (lisinopril and diketopiperazine) were resolved and their time-dependent relative contributions were also determined. Model-free and various model fitting methods were implemented in the kinetic analysis to estimate the activation energy of the intramolecular cyclization reaction. Arrhenius plots indicate that the activation energy is circa 327 kJ/mol.

The kinetics of the O2/CO2 reaction in molten carbonate - Reaction orders for O2 and CO2 on NiO. [in fuel cells

NASA Technical Reports Server (NTRS)

Winnick, J.; Ross, P. N.

1980-01-01

The kinetics of the O2/CO2 reaction in molten carbonate is investigated using paste electrolytes and nickel sinter electrodes. A two-step approach to the determination of reaction orders is employed. First, exchange currents at various P(CO2) and P(O2) were measured using the low polarization method. Second, alpha(+) and alpha(-) values were obtained from the slope of the Allen-Hickling plot for current densities low enough so that concentration polarization within the electrode can be neglected. The reaction orders are + 1/4 in CO2 and + 5/8 in O2 in the cathodic direction, and - 3/4 in CO2 and + 1/8 in O2 in the anodic direction.

Kinetics of Papain: An Introductory Biochemistry Laboratory Experiment

NASA Astrophysics Data System (ADS)

Cornely, Kathleen; Crespo, Eric; Earley, Michael; Kloter, Rachel; Levesque, Aime; Pickering, Mary

1999-05-01

Enzyme kinetics experiments are popular in the undergraduate laboratory. These experiments have pedagogic value because they reinforce the concepts of Michaelis-Menten kinetics covered in the lecture portion of the course and give students the experience of calculating kinetic constants from data they themselves have generated. In this experiment, we investigate the kinetics of the thiol protease papain. The source of the papain is commercially available papaya latex. A specific substrate, Na-benzoyl-arginine-p-nitroanilide (BAPNA), is used, which takes advantage of the fact that papain interacts with a phenylalanine residue two amino acids away from the peptide bond cleaved. Upon hydrolysis by papain, a bright yellow product is released, p-nitroaniline. This allows the reaction to be monitored spectrophotometrically by measuring the rate of formation of the p-nitroaniline product as a function of the increase in absorbance of the solution at the lmax of p-nitroaniline (400 nm) over time at various substrate concentrations. These data are used to plot a Lineweaver-Burk plot from which the vmax and KM are obtained. If time permits, students carry out additional investigations in which e of p-nitroaniline is measured, the enzyme solution protein concentration is measured, the enzyme purity is evaluated by SDS-PAGE, and a pH-rate profile is constructed from experimental data.

Albumin's Influence on Carprofen Enantiomers-Hymecromone Interaction.

PubMed

Tang, Mingjie; Guo, Yanjie; Gao, Youshui; Tang, Chao; Dang, Xiaoqian; Zhou, Zubin; Sun, Yuqiang; Wang, Kunzheng

2016-03-01

Hymecromone is an important coumarin drug, and carprofen is one of the most important nonsteroidal antiinflammatory drugs (NSAIDs). The present study aims to determine the influence of bovine serum albumin (BSA) on the carprofen-hymecromone interaction. The inhibition of carprofen enantiomers on the UDP-glucuronosyltransferase (UGT) 2B7-catalyzed glucuronidation of hymecromone was investigated in the UGTs incubation system with and without BSA. The inhibition capability of increased by 20% (P < 0.001) of (R)-carprofen after the addition of 0.5% BSA in the incubation mixture. In contrast, no significant difference was observed for the inhibition of (S)-carprofen on UGT2B7 activity in the absence or presence of 0.5% BSA in the incubation system. The Lineweaver-Burk plot showed that the intersection point was located in the vertical axis, indicating the competitive inhibition of (R)-carprofen on UGT2B7 in the incubation system with BSA, which is consistent with the inhibition kinetic type of (R)-carprofen on UGT2B7 in the incubation system without BSA. Furthermore, the second plot using the slopes from the Lineweaver-Burk versus the concentrations of (R)-carprofen showed that the fitting equation was y=39.997x+50. Using this equation, the inhibition kinetic parameter was calculated to be 1.3 μM. For (S)-carprofen, the intersection point was located in the horizontal axis in the Lineweaver-Burk plot for the incubation system with BSA, indicating the noncompetitive inhibition of (S)-carprofen on the activity of UGT2B7. The fitting plot of the second plot was y=24.6x+180, and the inhibition kinetic parameter was 7.3 μM. In conclusion, the present study gives a short summary of BSA's influence on the carprofen enantiomers-hymecromone interaction, which will guide the clinical application of carprofen and hymecromone. © 2015 Wiley Periodicals, Inc.

Measuring kinetics of complex single ion channel data using mean-variance histograms.

PubMed Central

Patlak, J B

1993-01-01

The measurement of single ion channel kinetics is difficult when those channels exhibit subconductance events. When the kinetics are fast, and when the current magnitudes are small, as is the case for Na+, Ca2+, and some K+ channels, these difficulties can lead to serious errors in the estimation of channel kinetics. I present here a method, based on the construction and analysis of mean-variance histograms, that can overcome these problems. A mean-variance histogram is constructed by calculating the mean current and the current variance within a brief "window" (a set of N consecutive data samples) superimposed on the digitized raw channel data. Systematic movement of this window over the data produces large numbers of mean-variance pairs which can be assembled into a two-dimensional histogram. Defined current levels (open, closed, or sublevel) appear in such plots as low variance regions. The total number of events in such low variance regions is estimated by curve fitting and plotted as a function of window width. This function decreases with the same time constants as the original dwell time probability distribution for each of the regions. The method can therefore be used: 1) to present a qualitative summary of the single channel data from which the signal-to-noise ratio, open channel noise, steadiness of the baseline, and number of conductance levels can be quickly determined; 2) to quantify the dwell time distribution in each of the levels exhibited. In this paper I present the analysis of a Na+ channel recording that had a number of complexities. The signal-to-noise ratio was only about 8 for the main open state, open channel noise, and fast flickers to other states were present, as were a substantial number of subconductance states. "Standard" half-amplitude threshold analysis of these data produce open and closed time histograms that were well fitted by the sum of two exponentials, but with apparently erroneous time constants, whereas the mean-variance histogram technique provided a more credible analysis of the open, closed, and subconductance times for the patch. I also show that the method produces accurate results on simulated data in a wide variety of conditions, whereas the half-amplitude method, when applied to complex simulated data shows the same errors as were apparent in the real data. The utility and the limitations of this new method are discussed. Images FIGURE 2 FIGURE 4 FIGURE 8 FIGURE 9 PMID:7690261

Choose Wisely: Static or Kinetic Friction--The Power of Dimensionless Plots

ERIC Educational Resources Information Center

Ludwigsen, Daniel; Svinarich, Kathryn

2009-01-01

Consider a problem of sliding blocks, one stacked atop the other, resting on a frictionless table. If the bottom block is pulled horizontally, nature makes a choice: if the applied force is small, static friction between the blocks accelerates the blocks together, but with a large force the blocks slide apart. In that case, kinetic friction still…

Catalytic site interactions in yeast OMP synthase.

PubMed

Hansen, Michael Riis; Barr, Eric W; Jensen, Kaj Frank; Willemoës, Martin; Grubmeyer, Charles; Winther, Jakob R

2014-01-15

The enigmatic kinetics, half-of-the-sites binding, and structural asymmetry of the homodimeric microbial OMP synthases (orotate phosphoribosyltransferase, EC 2.4.2.10) have been proposed to result from an alternating site mechanism in these domain-swapped enzymes [R.W. McClard et al., Biochemistry 45 (2006) 5330-5342]. This behavior was investigated in the yeast enzyme by mutations in the conserved catalytic loop and 5-phosphoribosyl-1-diphosphate (PRPP) binding motif. Although the reaction is mechanistically sequential, the wild-type (WT) enzyme shows parallel lines in double reciprocal initial velocity plots. Replacement of Lys106, the postulated intersubunit communication device, produced intersecting lines in kinetic plots with a 2-fold reduction of kcat. Loop (R105G K109S H111G) and PRPP-binding motif (D131N D132N) mutant proteins, each without detectable enzymatic activity and ablated ability to bind PRPP, complemented to produce a heterodimer with a single fully functional active site showing intersecting initial velocity plots. Equilibrium binding of PRPP and orotidine 5'-monophosphate showed a single class of two binding sites per dimer in WT and K106S enzymes. Evidence here shows that the enzyme does not follow half-of-the-sites cooperativity; that interplay between catalytic sites is not an essential feature of the catalytic mechanism; and that parallel lines in steady-state kinetics probably arise from tight substrate binding. Copyright © 2013. Published by Elsevier Inc.

Concentration-dependent photodegradation kinetics and hydroxyl-radical oxidation of phenicol antibiotics.

PubMed

Li, Kai; Zhang, Peng; Ge, Linke; Ren, Honglei; Yu, Chunyan; Chen, Xiaoyang; Zhao, Yuanfeng

2014-09-01

Thiamphenicol and florfenicol are two phenicol antibiotics widely used in aquaculture and are ubiquitous as micropollutants in surface waters. The present study investigated their photodegradation kinetics, hydroxyl-radical (OH) oxidation reactivities and products. Firstly, the photolytic kinetics of the phenicols in pure water was studied as a function of initial concentrations (C0) under UV-vis irradiation (λ>200nm). It was found that the kinetics was influenced by C0. A linear plot of the pseudo-first-order rate constant vs C0 was observed with a negative slope. Secondly, the reaction between the phenicol antibiotics and OH was examined with a competition kinetic method under simulated solar irradiation (λ>290nm), which quantified their bimolecular reaction rate constants of (2.13±0.02)×10(9)M(-1)s(-1) and (1.82±0.10)×10(9)M(-1)s(-1) for thiamphenicol and florfenicol, respectively. Then the corresponding OH oxidated half-lives in sunlit surface waters were calculated to be 90.5-106.1h. Some main intermediates were formed from the reaction, which suggested that the two phenicols underwent hydroxylation, oxygenation and dehydrogenation when OH existed. These results are of importance to assess the phenicol persistence in wastewater treatment and sunlit surface waters. Copyright © 2014 Elsevier Ltd. All rights reserved.

Biphasic Kinetic Behavior of E. coli WrbA, an FMN-Dependent NAD(P)H:Quinone Oxidoreductase

PubMed Central

Kishko, Iryna; Harish, Balasubramanian; Zayats, Vasilina; Reha, David; Tenner, Brian; Beri, Dhananjay; Gustavsson, Tobias; Ettrich, Rüdiger; Carey, Jannette

2012-01-01

The E. coli protein WrbA is an FMN-dependent NAD(P)H:quinone oxidoreductase that has been implicated in oxidative defense. Three subunits of the tetrameric enzyme contribute to each of four identical, cavernous active sites that appear to accommodate NAD(P)H or various quinones, but not simultaneously, suggesting an obligate tetramer with a ping-pong mechanism in which NAD departs before oxidized quinone binds. The present work was undertaken to evaluate these suggestions and to characterize the kinetic behavior of WrbA. Steady-state kinetics results reveal that WrbA conforms to a ping-pong mechanism with respect to the constancy of the apparent Vmax to Km ratio with substrate concentration. However, the competitive/non-competitive patterns of product inhibition, though consistent with the general class of bi-substrate reactions, do not exclude a minor contribution from additional forms of the enzyme. NMR results support the presence of additional enzyme forms. Docking and energy calculations find that electron-transfer-competent binding sites for NADH and benzoquinone present severe steric overlap, consistent with the ping-pong mechanism. Unexpectedly, plots of initial velocity as a function of either NADH or benzoquinone concentration present one or two Michaelis-Menten phases depending on the temperature at which the enzyme is held prior to assay. The effect of temperature is reversible, suggesting an intramolecular conformational process. WrbA shares these and other details of its kinetic behavior with mammalian DT-diaphorase, an FAD-dependent NAD(P)H:quinone oxidoreductase. An extensive literature review reveals several other enzymes with two-plateau kinetic plots, but in no case has a molecular explanation been elucidated. Preliminary sedimentation velocity analysis of WrbA indicates a large shift in size of the multimer with temperature, suggesting that subunit assembly coupled to substrate binding may underlie the two-plateau behavior. An additional aim of this report is to bring under wider attention the apparently widespread phenomenon of two-plateau Michaelis-Menten plots. PMID:22952804

Kinetic performance comparison of fully and superficially porous particles with a particle size of 5 µm: intrinsic evaluation and application to the impurity analysis of griseofulvin.

PubMed

Kahsay, Getu; Broeckhoven, Ken; Adams, Erwin; Desmet, Gert; Cabooter, Deirdre

2014-05-01

After the great commercial success of sub-3 µm superficially porous particles, vendors are now also starting to commercialize 5 µm superficially porous particles, as an alternative to their fully porous counterparts which are routinely used in pharmaceutical analysis. In this study, the performance of 5 µm superficially porous particles was compared to that of fully porous 5 µm particles in terms of efficiency, separation performance and loadability on a conventional HPLC instrument. Van Deemter and kinetic plots were first used to evaluate the efficiency and performance of both particle types using alkylphenones as a test mixture. The van Deemter and kinetic plots showed that the superficially porous particles provide a superior kinetic performance compared to the fully porous particles over the entire relevant range of separation conditions, when both support types were evaluated at the same operating pressure. The same observations were made both for isocratic and gradient analysis. The superior performance was further demonstrated for the separation of a pharmaceutical compound (griseofulvin) and its impurities, where a gain in analysis time of around 2 could be obtained using the superficially porous particles. Finally, both particle types were evaluated in terms of loadability by plotting the resolution of the active pharmaceutical ingredient and its closest impurity as a function of the signal-to-noise ratio obtained for the smallest impurity. It was demonstrated that the superficially porous particles show better separation performance for griseofulvin and its impurities without significantly compromising sensitivity due to loadability issues in comparison with their fully porous counterparts. Moreover these columns can be used on conventional equipment without modifications to obtain a significant improvement in analysis time. Copyright © 2014 Elsevier B.V. All rights reserved.

Persistence of oxyfluorfen in soil, runoff water, sediment and plants of a sunflower cultivation.

PubMed

Mantzos, N; Karakitsou, A; Hela, D; Patakioutas, G; Leneti, E; Konstantinou, I

2014-02-15

A field dissipation and transport study of oxyfluorfen in a sunflower cultivation under Mediterranean conditions have been conducted in silty clay plots (cultivated and uncultivated) with two surface slopes (1% and 5%). The soil dissipation and transport of oxyfluorfen in runoff water and sediment, as well as the uptake by sunflower plants, were investigated over a period of 191 days. Among different kinetic models assayed, soil dissipation rate of oxyfluorfen was better described by first-order kinetics. The average half-life was 45 and 45.5 days in cultivated plots with soil slopes 5% and 1% respectively, and 50.9 and 52.9 days in uncultivated plots with soil slopes 5% and 1%. The herbicide was detected below the 10 cm soil layer 45 days after application (DAA). Limited amounts of oxyfluorfen were moved with runoff water and the cumulative losses from tilled and untilled plots with slope 5% were estimated at 0.007% and 0.005% of the initial applied active ingredient, while for the plots with slope of 1%, the respective values were 0.002% and 0.001%. The maximum concentration of oxyfluorfen in sediment ranged from 1.46 μg g(-1) in cultivated plot with soil slope 1% to 2.33 μg g(-1) in uncultivated plot with soil slope 5%. The cumulative losses from tilled and untilled plots with slope 5% were estimated at 0.217% and 0.170% while for the plots with slope of 1%, the respective values were 0.055% and 0.025%. Oxyfluorfen was detected in sunflower plants until the day of harvest; maximum concentrations in stems and leaves (0.042 μg g(-1)) were observed 33 DAA and in roots (0.025 μg g(-1)) 36 DAA. In conclusion, oxyfluorfen hardly moves into silty clay soil and exhibited low run-off potential so it represents a low risk herbicide for the contamination of ground and adjacent water resources. Copyright © 2013 Elsevier B.V. All rights reserved.

Chaperonin-based biolayer interferometry to assess the kinetic stability of metastable, aggregation-prone proteins

PubMed Central

Lea, Wendy A.; Naik, Subhashchandra; Chaudhri, Tapan; Machen, Alexandra J.; O’Neil, Pierce T.; McGinn-Straub, Wesley; Tischer, Alexander; Auton, Matthew T.; Burns, Joshua R.; Baldwin, Michael R.; Khar, Karen R.; Karanicolas, John; Fisher, Mark T.

2017-01-01

Stabilizing the folded state of metastable and/or aggregation-prone proteins through exogenous ligand binding is an appealing strategy to decrease disease pathologies brought on by protein folding defects or deleterious kinetic transitions. Current methods of examining ligand binding to these marginally stable native states are limited, because protein aggregation typically interferes with analysis. Here, we describe a rapid method for assessing the kinetic stability of folded proteins and monitoring the effects of ligand stabilization for both intrinsically stable proteins (monomers, oligomers, multi-domain) and metastable proteins (e.g. low Tm) that uses a new GroEL chaperonin-based biolayer interferometry (BLI) denaturant-pulse platform. A kinetically controlled denaturation isotherm is generated by exposing a target protein immobilized on a BLI biosensor to increasing denaturant concentrations (urea or GnHCl) in a pulsatile manner to induce partial or complete unfolding of the attached protein population. Following the rapid removal of the denaturant, the extent of hydrophobic unfolded/partially folded species that remain is detected by increased GroEL binding. Since this kinetic denaturant pulse is brief, the amplitude of the GroEL binding to the immobilized protein depends on the duration of exposure to denaturant, the concentration of denaturant, wash times, and the underlying protein unfolding/refolding kinetics; fixing all other parameters and plotting GroEL binding amplitude versus denaturant pulse concentration results in a kinetically controlled denaturation isotherm. When folding osmolytes or stabilizing ligands are added to the immobilized target proteins before and during the denaturant pulse, the diminished population of unfolded/partially folded protein is manifested by a decreased GroEL binding and/or a marked shift in these kinetically controlled denaturation profiles to higher denaturant concentrations. This particular platform approach can be used to identify small molecules/solution conditions that can stabilize or destabilize thermally stable proteins, multi-domain proteins, oligomeric proteins, and most importantly, aggregation prone metastable proteins. PMID:27505032

Beta-oxidation as channeled reaction linked to citric acid cycle: evidence from measurements of mitochondrial pyruvate oxidation during fatty acid degradation.

PubMed

Förster, M E; Staib, W

1992-07-01

1. The kinetics of mitochondrial mammalian pyruvate dehydrogenase multienzyme complex (PDHC) is studied by the formation of CO2 using tracer amounts of [1-14C]pyruvate. It is found that the Hill plot results in a (pseudo-)cooperativity with a transition of n-1----3 at a pyruvate concentration about Ks. 2. Addition of L-carnitine, octanoate, palmitoyl-CoA or palmitate + L-carnitine + fatty acid-binding protein results in a Hill coefficient of n = 2 following the kinetics of pyruvate oxidation. 3. Addition of fatty acid-binding protein to an assay system oxidizing palmitate in presence of L-carnitine alters the pattern of the kinetics in the Hill plot so that an apparently lower level of L-carnitine is necessary for the reaction course of beta-degradation. 4. It is concluded that beta-degradation is a coordinated, multienzyme-complex based mechanism tightly linked to citric acid cycle and it is proposed that L-carnitine is actively involved into the reaction and not only functioning as carrier-molecule for transmembrane transport.

Kinetic operational models of agonism for G-protein-coupled receptors.

PubMed

Hoare, Samuel R J; Pierre, Nicolas; Moya, Arturo Gonzalez; Larson, Brad

2018-06-07

The application of kinetics to research and therapeutic development of G-protein-coupled receptors has become increasingly valuable. Pharmacological models provide the foundation of pharmacology, providing concepts and measurable parameters such as efficacy and potency that have underlain decades of successful drug discovery. Currently there are few pharmacological models that incorporate kinetic activity in such a way as to yield experimentally-accessible drug parameters. In this study, a kinetic model of pharmacological response was developed that provides a kinetic descriptor of efficacy (the transduction rate constant, k τ ) and allows measurement of receptor-ligand binding kinetics from functional data. The model assumes: (1) receptor interacts with a precursor of the response ("Transduction potential") and converts it to the response. (2) The response can decay. Familiar response vs time plots emerge, depending on whether transduction potential is depleted and/or response decays. These are the straight line, the "association" exponential curve, and the rise-and-fall curve. Convenient, familiar methods are described for measuring the model parameters and files are provided for the curve-fitting program Prism (GraphPad Software) that can be used as a guide. The efficacy parameter k τ is straightforward to measure and accounts for receptor reserve; all that is required is measurement of response over time at a maximally-stimulating concentration of agonist. The modular nature of the model framework allows it to be extended. Here this is done to incorporate antagonist-receptor binding kinetics and slow agonist-receptor equilibration. In principle, the modular framework can incorporate other cellular processes, such as receptor desensitization. The kinetic response model described here can be applied to measure kinetic pharmacological parameters than can be used to advance the understanding of GPCR pharmacology and optimize new and improved therapeutics. Copyright © 2018 Elsevier Ltd. All rights reserved.

Deducing the temporal order of cofactor function in ligand-regulated gene transcription: theory and experimental verification.

PubMed

Dougherty, Edward J; Guo, Chunhua; Simons, S Stoney; Chow, Carson C

2012-01-01

Cofactors are intimately involved in steroid-regulated gene expression. Two critical questions are (1) the steps at which cofactors exert their biological activities and (2) the nature of that activity. Here we show that a new mathematical theory of steroid hormone action can be used to deduce the kinetic properties and reaction sequence position for the functioning of any two cofactors relative to a concentration limiting step (CLS) and to each other. The predictions of the theory, which can be applied using graphical methods similar to those of enzyme kinetics, are validated by obtaining internally consistent data for pair-wise analyses of three cofactors (TIF2, sSMRT, and NCoR) in U2OS cells. The analysis of TIF2 and sSMRT actions on GR-induction of an endogenous gene gave results identical to those with an exogenous reporter. Thus new tools to determine previously unobtainable information about the nature and position of cofactor action in any process displaying first-order Hill plot kinetics are now available.

Deducing the Temporal Order of Cofactor Function in Ligand-Regulated Gene Transcription: Theory and Experimental Verification

PubMed Central

Dougherty, Edward J.; Guo, Chunhua; Simons, S. Stoney; Chow, Carson C.

2012-01-01

Cofactors are intimately involved in steroid-regulated gene expression. Two critical questions are (1) the steps at which cofactors exert their biological activities and (2) the nature of that activity. Here we show that a new mathematical theory of steroid hormone action can be used to deduce the kinetic properties and reaction sequence position for the functioning of any two cofactors relative to a concentration limiting step (CLS) and to each other. The predictions of the theory, which can be applied using graphical methods similar to those of enzyme kinetics, are validated by obtaining internally consistent data for pair-wise analyses of three cofactors (TIF2, sSMRT, and NCoR) in U2OS cells. The analysis of TIF2 and sSMRT actions on GR-induction of an endogenous gene gave results identical to those with an exogenous reporter. Thus new tools to determine previously unobtainable information about the nature and position of cofactor action in any process displaying first-order Hill plot kinetics are now available. PMID:22272313

Correlated electron and nuclear dynamics in strong field photoionization of H(2)(+).

PubMed

Silva, R E F; Catoire, F; Rivière, P; Bachau, H; Martín, F

2013-03-15

We present a theoretical study of H(2)(+) ionization under strong IR femtosecond pulses by using a method designed to extract correlated (2D) photoelectron and proton kinetic energy spectra. The results show two distinct ionization mechanisms-tunnel and multiphoton ionization-in which electrons and nuclei do not share the energy from the field in the same way. Electrons produced in multiphoton ionization share part of their energy with the nuclei, an effect that shows up in the 2D spectra in the form of energy-conservation fringes similar to those observed in weak-field ionization of diatomic molecules. In contrast, tunneling electrons lead to fringes whose position does not depend on the proton kinetic energy. At high intensity, the two processes coexist and the 2D plots show a very rich behavior, suggesting that the correlation between electron and nuclear dynamics in strong field ionization is more complex than one would have anticipated.

Growth kinetics of gamma-prime precipitates in a directionally solidified eutectic, gamma/gamma-prime-delta

NASA Technical Reports Server (NTRS)

Tewari, S. N.

1976-01-01

A directionally solidified eutectic alloy (DSEA), of those viewed as potential candidates for the next generation of aircraft gas turbine blade materials, is studied for the gamma-prime growth kinetics, in the system Ni-Nb-Cr-Al, specifically: Ni-20 w/o Nb-6 w/o Cr-2.5 w/o Al gamma/gamma-prime-delta DSEA. Heat treatment, polishing and etching, and preparation for electron micrography are described, and the size distribution of gamma-prime phase following various anneals is plotted, along with gamma-prime growth kinetics in this specific DSEA, and the cube of gamma-prime particle size vs anneal time. Activation energies and coarsening kinetics are studied.

Turbulence model sensitivity and scour gap effect of unsteady flow around pipe: a CFD study.

PubMed

Ali, Abbod; Sharma, R K; Ganesan, P; Akib, Shatirah

2014-01-01

A numerical investigation of incompressible and transient flow around circular pipe has been carried out at different five gap phases. Flow equations such as Navier-Stokes and continuity equations have been solved using finite volume method. Unsteady horizontal velocity and kinetic energy square root profiles are plotted using different turbulence models and their sensitivity is checked against published experimental results. Flow parameters such as horizontal velocity under pipe, pressure coefficient, wall shear stress, drag coefficient, and lift coefficient are studied and presented graphically to investigate the flow behavior around an immovable pipe and scoured bed.

Proceedings of the U.S. Army Symposium on Gun Dynamics (4th) Held at Riviera Beach, Florida on 7-9 May 1985. Volume 2

DTIC Science & Technology

1985-05-01

the linear or non linear force is applied to it. This also means that both the potentidl and kinetic energies are the same for the "real" and the...are taken up and rebound occurs. With long rod kinetic energy ammunition, this response is supplemented by longitudinal flexure of the sabot and of...generic kinetic energy projectile is plotted as a function of launch velocity in Figure 4. The deflection in mils is ratiocd by the launch angle of

Short communication: Glucose kinetics in dairy heifers limit-fed a low- or high-forage ration at four levels of nitrogen intake

USDA-ARS?s Scientific Manuscript database

The objective of this research was to evaluate the effect of level of forage and nitrogen (N) intake on glucose kinetics in growing dairy heifers. Eight Holstein heifers (beginning at 362 ± 7 kg body weight (BW) and 12.3 ± 0.4 months of age) were fed eight rations according to a split-plot, 4 x 4 La...

SU-D-207A-02: Possible Characterization of the Brain Tumor Vascular Environment by a Novel Strategy of Quantitative Analysis in Dynamic Contrast Enhanced MR Imaging: A Combination of Both Patlak and Logan Analyses

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

Yee, S; Chinnaiyan, P; Wloch, J

Purpose: The majority of quantitative analyses involving dynamic contrast enhanced (DCE) MRI have been performed to obtain kinetic parameters such as Ktrans and ve. Such analyses are generally performed assuming a “reversible” tissue compartment, where the tracer is assumed to be rapidly equilibrated between the plasma and tissue compartments. However, some tumor vascular environments may be more suited for a “non-reversible” tissue compartment, where, as with FDG PET imaging, the tracer is continuously deposited into the tissue compartment (or the return back to the plasma compartment is very slow in the imaging time scale). Therefore, Patlak and Logan analyses, whichmore » represent tools for the “non-reversible” and “reversible” modeling, respectively, were performed to better characterize the brain tumor vascular environment. Methods: A voxel-by-voxel analysis was performed to generate both Patlak and Logan plots in two brain tumor patients, one with grade III astrocytoma and the other with grade IV astrocytoma or glioblastoma. The slopes of plots and the r-square were then obtained by linear fitting and compared for each voxel. Results: The 2-dimensional scatter plots of Logan (Y-axis) vs. Patlak slopes (X-axis) clearly showed increased Logan slopes for glioblastoma (Figure 3A). The scatter plots of goodness-of-fit (Figure 3B) also suggested glioblastoma, relative to grade III astrocytoma, might consist of more voxels that are kinetically Logan-like (i.e. rapidly equilibrated extravascular space and active vascular environment). Therefore, the enhanced Logan-like behavior (and the Logan slope) in glioblastoma may imply an increased fraction of active vascular environment, while the enhanced Patlak-like behavior implies the vascular environment permitting a relatively slower washout of the tracer. Conclusion: Although further verification is required, the combination of Patlak and Logan analyses in DCE MRI may be useful in characterizing the tumor vascular environment, and thus, may have implications in tumor grading and monitoring response to anti-vascular therapy.« less

A novel determination of calcite dissolution kinetics in seawater

NASA Astrophysics Data System (ADS)

Subhas, Adam V.; Rollins, Nick E.; Berelson, William M.; Dong, Sijia; Erez, Jonathan; Adkins, Jess F.

2015-12-01

We present a novel determination of the dissolution kinetics of inorganic calcite in seawater. We dissolved 13 C -labeled calcite in unlabeled seawater, and traced the evolving δ13 C composition of the fluid over time to establish dissolution rates. This method provides sensitive determinations of dissolution rate, which we couple with tight constraints on both seawater saturation state and surface area of the dissolving minerals. We have determined dissolution rates for two different abiotic calcite materials and three different grain sizes. Near-equilibrium dissolution rates are highly nonlinear, and are well normalized by geometric surface area, giving an empirical dissolution rate dependence on saturation state (Ω) of: This result substantiates the non-linear response of calcite dissolution to undersaturation. The bulk dissolution rate constant calculated here is in excellent agreement with those determined in far from equilibrium and dilute solution experiments. Plots of dissolution versus undersaturation indicates the presence of at least two dissolution mechanisms, implying a criticality in the calcite-seawater system. Finally, our new rate determination has implications for modeling of pelagic and seafloor dissolution. Nonlinear dissolution kinetics in a simple 1-D lysocline model indicate a possible transition from kinetic to diffusive control with increasing water depth, and also confirm the importance of respiration-driven dissolution in setting the shape of the calcite lysocline.

Recovery of Whey Proteins and Enzymatic Hydrolysis of Lactose Derived from Casein Whey Using a Tangential Flow Ultrafiltration Module

NASA Astrophysics Data System (ADS)

Das, Bipasha; Bhattacharjee, Sangita; Bhattacharjee, Chiranjib

2013-09-01

In this study, ultrafiltration (UF) of pretreated casein whey was carried out in a cross-flow module fitted with 5 kDa molecular weight cut-off polyethersulfone membrane to recover whey proteins in the retentate and lactose in the permeate. Effects of processing conditions, like transmembrane pressure and pH on permeate flux and rejection were investigated and reported. The polarised layer resistance was found to increase with time during UF even in this high shear device. The lactose concentration in the permeate was measured using dinitro salicylic acid method. Enzymatic kinetic study for lactose hydrolysis was carried out at three different temperatures ranging from 30 to 50 °C using β-galactosidase enzyme. The glucose formed during lactose hydrolysis was analyzed using glucose oxidase-peroxidase method. Kinetics of enzymatic hydrolysis of lactose solution was found to follow Michaelis-Menten model and the model parameters were estimated by Lineweaver-Burk plot. The hydrolysis rate was found to be maximum (with Vmax = 5.5091 mmol/L/min) at 30 °C.

Pyrolysis of Musa balbisiana flower petal using thermogravimetric studies.

PubMed

Sriram, Aswin; Swaminathan, Ganapathiraman

2018-05-11

In the present study, thermogravimetric analysis of Musa balbisiana flower petal was carried out to study the degradation behaviour and the kinetics in the pyrolytic reaction. The pyrolysis was carried out in the temperature range of 35-900 °C at different heating rates of 5, 10 and 20 °C/min. The kinetics was investigated using different models like Kissinger-Akahira-Sunose (KAS), Flynn-Ozawa-Wall (FOW), Friedman and Broido's plot. The average E a values determined by KAS, FOW and Friedman methods were 137.94, 136.76 and 133.36 kJ/mol respectively. Coats-Redfern method was utilized to determine the pre-exponential factors and the reaction order of the pyrolysis. For the conversion rates 0.1 and 0.2, both Valensi and Ginstling diffusion models were found out to be appropriate for the solid state reaction mechanism. The HHV of Musa balbisiana flower petal was 16.35 MJ/kg, suggested as a potential bio-feedstock energy source from agro-waste. Copyright © 2018. Published by Elsevier Ltd.

Lack of dose dependent kinetics of methyl salicylate-2-O-β-D-lactoside in rhesus monkeys after oral administration.

PubMed

He, Yangyang; Yan, Yu; Zhang, Tiantai; Ma, Yinzhong; Zhang, Wen; Wu, Ping; Song, Junke; Wang, Shuang; Du, Guanhua

2015-04-22

Methyl salicylate-2-O-β-d-lactoside (MSL) is one of the main active components isolated from Gaultheria yunnanensis, which is a traditional Chinese medicine used to treat arthritis and various aches and pains. Pharmacological researches showed that MSL had various effective activities in both in vivo and in vitro experiments. However, the pharmacokinetics features and oral bioavailability of MSL in primates were not studied up to now. To study the pharmacokinetics of different doses of MSL in rhesus monkeys and investigate the absolute bioavailability of MSL after oral administration. Male and female rhesus monkeys were either orally administrated with MSL 200, 400 and 800 mg/kg or received an intravenous dose of 20mg/kg randomly. The levels of MSL and salicylic acid (SA) in plasma were simultaneous measured by a simple, sensitive and reproducible high performance liquid chromatography method. Mean peak plasma concentration values for groups treated with 200, 400 and 800 mg/kg doses ranged from 48.79 to 171.83 μg/mL after single-dose oral administration of MSL, and mean area under the concentration-time curve values ranged from 195.16 to 1107.76 μg/mL h. Poor linearity of the kinetics of SA after oral administration of MSL was observed in the regression analysis of the Cmax-dose plot (r(2)=0.812), CL-dose plot (r(2)=0.225) and AUC(0-t)-dose plot (r(2)=0.938). Absolute bioavailability of MSL was assessed to be 118.89 ± 57.50, 213.54 ± 58.98 and 168.72 ± 76.58%, respectively. Bioavailability of MSL after oral administration in rhesus monkeys was measured for the first time. Pharmacokinetics parameters did not appear to be dose proportional among the three oral doses of treatments, and MSL showed an apparent absolute bioavailability in excess of 100% in rhesus monkeys based on the present study. In addition, a rapid, sensitive and reliable HPLC method was established and demonstrated for the research of traditional Chinese medicine in this study. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Effects of grain source, grain processing, and protein degradability on rumen kinetics and microbial protein synthesis in Boer kids.

PubMed

Brassard, M-E; Chouinard, P Y; Berthiaume, R; Tremblay, G F; Gervais, R; Martineau, R; Cinq-Mars, D

2015-11-01

Microbial protein synthesis in the rumen would be optimized when dietary carbohydrates and proteins have synchronized rates and extent of degradation. The aim of this study was to evaluate the effect of varying ruminal degradation rate of energy and nitrogen sources on intake, nitrogen balance, microbial protein yield, and kinetics of nutrients in the rumen of growing kids. Eight Boer goats (38.2 ± 3.0 kg) were used. The treatments were arranged in a split-plot Latin square design with grain sources (barley or corn) forming the main plots (squares). Grain processing methods and levels of protein degradability formed the subplots in a 2 × 2 factorial arrangement for a total of 8 dietary treatments. The grain processing method was rolling for barley and cracking for corn. Levels of protein degradability were obtained by feeding untreated soybean meal (SBM) or heat-treated soybean meal (HSBM). Each experimental period lasted 21 d, consisting of a 10-d adaptation period, a 7-d digestibility determination period, and a 4-d rumen evacuation and sampling period. Kids fed with corn had higher purine derivatives (PD) excretion when coupled with SBM compared with HSBM and the opposite occurred with barley-fed kids ( ≤ 0.01). Unprocessed grain offered with SBM led to higher PD excretion than with HSBM whereas protein degradability had no effect when processed grain was fed ( ≤ 0.03). Results of the current experiment with high-concentrate diets showed that microbial N synthesis could be maximized in goat kids by combining slowly fermented grains (corn or unprocessed grains) with a highly degradable protein supplement (SBM). With barley, a more rapidly fermented grain, a greater microbial N synthesis was observed when supplementing a low-degradable protein (HSBM).

Identifying the proton transfer reaction mechanism via a proton-bound dimeric intermediate for esomeprazoles by a kinetic method combined with density functional theory calculations.

PubMed

Cao, Xiaoji; Zhang, Feifei; Zhu, Kundan; Ye, Xuemin; Shen, Lingxiao; Chen, Jiaoyu; Mo, Weimin

2014-05-15

Esomeprazole analogs are a class of important proton pump inhibitors for the treatment of gastro-esophageal reflux diseases. Understanding the fragmentation reaction mechanism of the protonated esomeprazole analogs will facilitate the characterization of their complex metabolic fate in humans. In this paper, the kinetic method and theoretical calculations were applied to evaluate the fragmentation of protonated esomeprazole analogs. All collision-induced dissociation (CID) mass spectrometry experiments were carried out using electrospray ionization (ESI) ion trap mass spectrometry in positive ion mode. Also the accurate masses of fragments were measured on by ESI quadrupole time-of-flight (QTOF) MS in positive ion mode. Theoretical calculations were carried out by the density functional theory (DFT) method with the 6-31G(d) basis set in the Gaussian 03 program. In the fragmentation of the protonated esomeprazole analogs, C-S bond breakage is observed, which gives rise to protonated 2-(sulfinylmethylene)pyridines and protonated benzimidazoles. DFT calculations demonstrate that the nitrogen atom of the pyridine part is the thermodynamically most favorable protonation site, and the C-S bond cleavage is triggered by the transfer of this ionizing proton from the nitrogen atom of the pyridine part to the carbon atom of the benzimidazole part to which the sulfinyl is attached. Moreover, with the kinetic plot, the intensity ratios of two protonated product ions yield a linear relationship with the differences in proton affinities of the corresponding neutral molecules, which provides strong experimental evidence that the reaction proceeds via proton-bound 2-(sulfinylmethylene)pyridine/benzimidazole complex intermediates. The kinetic method combined with theoretical calculations was successfully applied to probe the proton transfer reaction by proton-bound 2-(sulfinylmethylene)pyridine/benzimidazole complexes in the fragmentation of protonated esomeprazole analogs by ESI CID MS, which is a strong evidence that the kinetic method can be applied in identifying a proton-bound dimeric intermediate in the fragmentation of protonated ions. Copyright © 2014 John Wiley & Sons, Ltd.

Quantification and evaluation of kinetic bio-catalytic pathway of horseradish peroxidase in an electron mediated reaction system and its applications in plant extracts.

PubMed

Krishna, Honnur; Nagaraja, Padmarajaiah; Shivakumar, Anantharaman; Chamaraja, Nelligere A; Aradhana, Narayan

2013-02-01

The intermolecular coupling of 2,5-dimethoxyaniline (DMA) as mediated electron transfer reaction in presence of H(2)O(2) and peroxidase in acetate buffer of pH 4.2 resulting green colored product having maximum absorption at λ(max)=740 nm was investigated by spectrophotometer. Under optimum conditions, linearity range for the quantification of H(2)O(2) was 2.0-288.0 μM and for peroxidase were 0.59-9.46 and 0.443-9.46 nM by kinetic and fixed-time method, respectively. The catalytic efficiency and catalytic power were K(eff)(D)=2.354 × 10(5)M(-1)min(-1) and K(pow)(D)=4.59 × 10(-4)min(-1), respectively. From the plot of d(1/D(o)) vs d(1/V(o)) and d(1/H(o)) vs d(1/V(o)), Michaelis-Menten constants for DMA and H(2)O(2)were found that K(m)(D)=1,458 μM and [Formula: see text] =301 μM. Applicability of the method was tested for peroxidase activity in some plant extracts and compared with guaiacol/peroxidase system. Regarding superiority of the method, it is suggested that DMA/peroxidase system can be a better hydrogen donor for HRP assay than guaiacol system as evident from kinetic data. Copyright © 2012 Elsevier B.V. All rights reserved.

Growth Kinetics of Extremely Halophilic Archaea (Family Halobacteriaceae) as Revealed by Arrhenius Plots

PubMed Central

Robinson, Jessie L.; Pyzyna, Brandy; Atrasz, Rachelle G.; Henderson, Christine A.; Morrill, Kira L.; Burd, Anna Mae; DeSoucy, Erik; Fogleman, Rex E.; Naylor, John B.; Steele, Sarah M.; Elliott, Dawn R.; Leyva, Kathryn J.; Shand, Richard F.

2005-01-01

Members of the family Halobacteriaceae in the domain Archaea are obligate extreme halophiles. They occupy a variety of hypersaline environments, and their cellular biochemistry functions in a nearly saturated salty milieu. Despite extensive study, a detailed analysis of their growth kinetics is missing. To remedy this, Arrhenius plots for 14 type species of the family were generated. These organisms had maximum growth temperatures ranging from 49 to 58°C. Nine of the organisms exhibited a single temperature optimum, while five grew optimally at more than one temperature. Generation times at these optimal temperatures ranged from 1.5 h (Haloterrigena turkmenica) to 3.0 h (Haloarcula vallismortis and Halorubrum saccharovorum). All shared an inflection point at 31 ± 4°C, and the temperature characteristics for 12 of the 14 type species were nearly parallel. The other two species (Natronomonas pharaonis and Natronorubrum bangense) had significantly different temperature characteristics, suggesting that the physiology of these strains is different. In addition, these data show that the type species for the family Halobacteriaceae share similar growth kinetics and are capable of much faster growth at higher temperatures than those previously reported. PMID:15659670

Homogeneous Molecular Catalysis of Electrochemical Reactions: Catalyst Benchmarking and Optimization Strategies.

PubMed

Costentin, Cyrille; Savéant, Jean-Michel

2017-06-21

Modern energy challenges currently trigger an intense interest in catalysis of redox reactions-electrochemical and photochemical-particularly those involving small molecules such as water, hydrogen, oxygen, proton, carbon dioxide. A continuously increasing number of molecular catalysts of these reactions, mostly transition metal complexes, have been proposed, rendering necessary procedures for their rational benchmarking and fueling the quest for leading principles that could inspire the design of improved catalysts. The search of "volcano plots" correlating catalysis kinetics to the stability of the key intermediate is a popular approach to the question in catalysis by surface-active sites, with as foremost example the electrochemical reduction of aqueous proton on metal surfaces. We discussed here for the first time, on theoretical and experimental grounds, the pertinence of such an approach in the field of molecular catalysis. This is the occasion to insist on the virtue of careful mechanism assignments. Particular emphasis is put on the interest of expressing the catalysts' intrinsic kinetic properties by means of catalytic Tafel plots, which relate kinetics and overpotential. We also underscore that the principle and strategies put forward for the catalytic activation of the above-mentioned small molecules are general as illustrated by catalytic applications out of this particular field.

Turbulence Model Sensitivity and Scour Gap Effect of Unsteady Flow around Pipe: A CFD Study

PubMed Central

Ali, Abbod; Sharma, R. K.; Ganesan, P.

2014-01-01

A numerical investigation of incompressible and transient flow around circular pipe has been carried out at different five gap phases. Flow equations such as Navier-Stokes and continuity equations have been solved using finite volume method. Unsteady horizontal velocity and kinetic energy square root profiles are plotted using different turbulence models and their sensitivity is checked against published experimental results. Flow parameters such as horizontal velocity under pipe, pressure coefficient, wall shear stress, drag coefficient, and lift coefficient are studied and presented graphically to investigate the flow behavior around an immovable pipe and scoured bed. PMID:25136666

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.

RAMONA-4B a computer code with three-dimensional neutron kinetics for BWR and SBWR system transient - user`s manual

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

Rohatgi, U.S.; Cheng, H.S.; Khan, H.J.

This document is the User`s Manual for the Boiling Water Reactor (BWR), and Simplified Boiling Water Reactor (SBWR) systems transient code RAMONA-4B. The code uses a three-dimensional neutron-kinetics model coupled with a multichannel, nonequilibrium, drift-flux, phase-flow model of the thermal hydraulics of the reactor vessel. The code is designed to analyze a wide spectrum of BWR core and system transients. Chapter 1 gives an overview of the code`s capabilities and limitations; Chapter 2 describes the code`s structure, lists major subroutines, and discusses the computer requirements. Chapter 3 is on code, auxillary codes, and instructions for running RAMONA-4B on Sun SPARCmore » and IBM Workstations. Chapter 4 contains component descriptions and detailed card-by-card input instructions. Chapter 5 provides samples of the tabulated output for the steady-state and transient calculations and discusses the plotting procedures for the steady-state and transient calculations. Three appendices contain important user and programmer information: lists of plot variables (Appendix A) listings of input deck for sample problem (Appendix B), and a description of the plotting program PAD (Appendix C). 24 refs., 18 figs., 11 tabs.« less

Enzyme Kinetics: The Use of Amylose Azure.

ERIC Educational Resources Information Center

Cusimano, Vincent J.

1978-01-01

Amylose azure can be used as a chromogenic substrate for alpha-amylase in studying the effects of temperature and pH enzyme action. This is a model system which students can use to measure the energy of activation using the Arrhenius plot. (Author/BB)

A New Kinetic Spectrophotometric Method for the Quantitation of Amorolfine.

PubMed

Soto, César; Poza, Cristian; Contreras, David; Yáñez, Jorge; Nacaratte, Fallon; Toral, M Inés

2017-01-01

Amorolfine (AOF) is a compound with fungicide activity based on the dual inhibition of growth of the fungal cell membrane, the biosynthesis and accumulation of sterols, and the reduction of ergosterol. In this work a sensitive kinetic and spectrophotometric method for the AOF quantitation based on the AOF oxidation by means of KMnO 4 at 30 min (fixed time), pH alkaline, and ionic strength controlled was developed. Measurements of changes in absorbance at 610 nm were used as criterion of the oxidation progress. In order to maximize the sensitivity, different experimental reaction parameters were carefully studied via factorial screening and optimized by multivariate method. The linearity, intraday, and interday assay precision and accuracy were determined. The absorbance-concentration plot corresponding to tap water spiked samples was rectilinear, over the range of 7.56 × 10 -6 -3.22 × 10 -5  mol L -1 , with detection and quantitation limits of 2.49 × 10 -6  mol L -1 and 7.56 × 10 -6  mol L -1 , respectively. The proposed method was successfully validated for the application of the determination of the drug in the spiked tap water samples and the percentage recoveries were 94.0-105.0%. The method is simple and does not require expensive instruments or complicated extraction steps of the reaction product.

Radiation-induced controlled polymerization of acrylic acid by RAFT and RAFT-MADIX methods in protic solvents

NASA Astrophysics Data System (ADS)

Sütekin, S. Duygu; Güven, Olgun

2018-01-01

The kinetic investigation of one-pot synthesis of poly(acrylic acid) (PAA) prepared via gamma radiation induced controlled polymerization was reported. PAA homopolymers were prepared by Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization in the presence of trithiocarbonate-based chain transfer agent (CTA) 2-(Dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) and also by Reversible Addition-Fragmentation/Macromolecular Design by Inter-change of Xanthates (RAFT/MADIX) polymerization in the presence of a xanthate based CTA O-ethyl-S-(1-methoxycarbonyl) ethyl dithiocarbonate (RA1). The polymerizations were performed at room temperature by the virtue of ionizing radiation. Protic solvents were used for the RAFT polymerization of AA considering environmental profits. The linear first-order kinetic plot, close control of molecular weight by the monomer/CTA molar ratio supported that the polymerization proceeds in a living fashion. The linear increase in molecular weight with conversion monitored by Size Exclusion Chromatography (SEC) is another proof of controlling of polymerization. [Monomer]/[RAFT] ratio and conversion was controlled to obtain PAA in the molecular weight range of 6900-35,800 with narrow molecular weight distributions. Reaction kinetics and effect of the amount of RAFT agent were investigated in detail. Between two different types of CTA, trithiocarbonate based DDMAT was found to be more efficient in terms of low dispersity (Đ) and linear first-order kinetic behavior for the radiation induced controlled synthesis of PAA homopolymers.

A time to search: finding the meaning of variable activation energy.

PubMed

Vyazovkin, Sergey

2016-07-28

This review deals with the phenomenon of variable activation energy frequently observed when studying the kinetics in the liquid or solid phase. This phenomenon commonly manifests itself through nonlinear Arrhenius plots or dependencies of the activation energy on conversion computed by isoconversional methods. Variable activation energy signifies a multi-step process and has a meaning of a collective parameter linked to the activation energies of individual steps. It is demonstrated that by using appropriate models of the processes, the link can be established in algebraic form. This allows one to analyze experimentally observed dependencies of the activation energy in a quantitative fashion and, as a result, to obtain activation energies of individual steps, to evaluate and predict other important parameters of the process, and generally to gain deeper kinetic and mechanistic insights. This review provides multiple examples of such analysis as applied to the processes of crosslinking polymerization, crystallization and melting of polymers, gelation, and solid-solid morphological and glass transitions. The use of appropriate computational techniques is discussed as well.

A new approach for development of kinetics of wastewater treatment in aerobic biofilm reactor

NASA Astrophysics Data System (ADS)

Goswami, S.; Sarkar, S.; Mazumder, D.

2017-09-01

Biofilm process is widely used for the treatment of a variety of wastewater especially containing slowly biodegradable substances. It provides resistance against toxic environment and is capable of retaining biomass under continuous operation. Development of kinetics is very much pertinent for rational design of a biofilm process for the treatment of wastewater with or without inhibitory substances. A simple approach for development of such kinetics for an aerobic biofilm reactor has been presented using a novel biofilm model. The said biofilm model is formulated from the correlations between substrate concentrations in the influent/effluent and at biofilm liquid interface along with substrate flux and biofilm thickness complying Monod's growth kinetics. The methodology for determining the kinetic coefficients for substrate removal and biomass growth has been demonstrated stepwise along with graphical representations. Kinetic coefficients like K, k, Y, b t, b s, and b d are determined either from the intercepts of X- and Y-axis or from the slope of the graphical plots.

Auger parameter and Wagner plot studies of small copper clusters

NASA Astrophysics Data System (ADS)

Moretti, Giuliano; Palma, Amedeo; Paparazzo, Ernesto; Satta, Mauro

2016-04-01

We discuss application of the Auger parameter and Wagner plot concepts to the study of small copper clusters deposited on various supports such as C(graphite), SiO2 and Al2O3. We demonstrate that the cluster size and the electronic properties of the support influence the shifts of both the binding energy of the Cu 2p3/2 transition and the kinetic energy of the Cu L3M45M45; 1G Auger transition. We find that the Cu L3M45M45; 1G-2p3/2 Auger parameter and Wagner plot allow one to single out and measure both initial- and final-state effects with a detail which is superior to that achieved in photoemission studies.

The analysis and kinetic energy balance of an upper-level wind maximum during intense convection

NASA Technical Reports Server (NTRS)

Fuelberg, H. E.; Jedlovec, G. J.

1982-01-01

The purpose of this paper is to analyze the formation and maintenance of the upper-level wind maximum which formed between 1800 and 2100 GMT, April 10, 1979, during the AVE-SESAME I period, when intense storms and tornadoes were experienced (the Red River Valley tornado outbreak). Radiosonde stations participating in AVE-SESAME I are plotted (centered on Oklahoma). National Meteorological Center radar summaries near the times of maximum convective activity are mapped, and height and isotach plots are given, where the formation of an upper-level wind maximum over Oklahoma is the most significant feature at 300 mb. The energy balance of the storm region is seen to change dramatically as the wind maximum forms. During much of its lifetime, the upper-level wind maximum is maintained by ageostrophic flow that produces cross-contour generation of kinetic energy and by the upward transport of midtropospheric energy. Two possible mechanisms for the ageostrophic flow are considered.

Quantitative production of compound I from a cytochrome P450 enzyme at low temperatures. Kinetics, activation parameters, and kinetic isotope effects for oxidation of benzyl alcohol.

PubMed

Wang, Qin; Sheng, Xin; Horner, John H; Newcomb, Martin

2009-08-05

Cytochrome P450 enzymes are commonly thought to oxidize substrates via an iron(IV)-oxo porphyrin radical cation transient termed Compound I, but kinetic studies of P450 Compounds I are essentially nonexistent. We report production of Compound I from cytochrome P450 119 (CYP119) in high conversion from the corresponding Compound II species at low temperatures in buffer mixtures containing 50% glycerol by photolysis with 365 nm light from a pulsed lamp. Compound I was studied as a reagent in oxidations of benzyl alcohol and its benzylic mono- and dideuterio isotopomers. Pseudo-first-order rate constants obtained at -50 degrees C with concentrations of substrates between 1.0 and 6.0 mM displayed saturation kinetics that gave binding constants for the substrate in the Compound I species (K(bind)) and first-order rate constants for the oxidation reactions (k(ox)). Representative results are K(bind) = 214 M(-1) and k(ox) = 0.48 s(-1) for oxidation of benzyl alcohol. For the dideuterated substrate C(6)H(5)CD(2)OH, kinetics were studied between -50 and -25 degrees C, and a van't Hoff plot for complexation and an Arrhenius plot for the oxidation reaction were constructed. The H/D kinetic isotope effects (KIEs) at -50 degrees C were resolved into a large primary KIE (P = 11.9) and a small, inverse secondary KIE (S = 0.96). Comparison of values extrapolated to 22 degrees C of both the rate constant for oxidation of C(6)H(5)CD(2)OH and the KIE for the nondeuterated and dideuterated substrates to values obtained previously in laser flash photolysis experiments suggested that tunneling could be a significant component of the total rate constant at -50 degrees C.

Competition kinetics using the UV/H2O2 process: a structure reactivity correlation for the rate constants of hydroxyl radicals toward nitroaromatic compounds.

PubMed

García Einschlag, Fernando S; Carlos, Luciano; Capparelli, Alberto L

2003-10-01

The rate constants for hydroxyl radical reaction toward a set of nitroaromatic substrates kS, have been measured at 25 degrees C using competition experiments in the UV/H2O2 process. For a given pair of substrates S1 and S2, the relative reactivity beta (defined as kS1/kS2) was calculated from the slope of the corresponding double logarithmic plot, i.e., of ln[S1] vs. ln[S2]. This method is more accurate and remained linear for larger conversions in comparison with the plots of ln[S1] and ln[S2] against time. The rate constants measured ranged from 0.33 to 8.6 x 10(9) M(-1)s(-1). A quantitative structure-reactivity relationship was found using the Hammett equation. Assuming sigma values to be additive, a value of -0.60 was obtained for the reaction constant rho. This value agrees with the high reactivity and the electrophilic nature of HO* radical.

A STATISTICAL STUDY OF THE SOLAR WIND TURBULENCE AT ION KINETIC SCALES USING THE K-FILTERING TECHNIQUE AND CLUSTER DATA

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

Roberts, O. W.; Li, X.; Jeska, L., E-mail: o.wyn.roberts@gmail.com, E-mail: xxl@aber.ac.uk

2015-03-20

Plasma turbulence at ion kinetic scales in the solar wind is investigated using the multi-point magnetometer data from the Cluster spacecraft. By applying the k-filtering method, we are able to estimate the full three-dimensional power spectral density P(ω{sub sc}, k) at a certain spacecraft frequency ω{sub sc} in wavevector (k) space. By using the wavevector at the maximum power in P(ω{sub sc}, k) at each sampling frequency ω{sub sc} and the Doppler shifted frequency ω{sub pla} in the solar wind frame, the dispersion plot ω{sub pla} = ω{sub pla}(k) is found. Previous studies have been limited to very few intervalsmore » and have been hampered by large errors, which motivates a statistical study of 52 intervals of solar wind. We find that the turbulence is predominantly highly oblique to the magnetic field k >> k {sub ∥}, and propagates slowly in the plasma frame with most points having frequencies smaller than the proton gyrofrequency ω{sub pla} < Ω{sub p}. Weak agreement is found that turbulence at the ion kinetic scales consists of kinetic Alfvén waves and coherent structures advected with plasma bulk velocity plus some minor more compressible components. The results suggest that anti-sunward and sunward propagating magnetic fluctuations are of similar nature in both the fast and slow solar wind at ion kinetic scales. The fast wind has significantly more anti-sunward flux than sunward flux and the slow wind appears to be more balanced.« less

Investigation of catalytic activity towards oxygen reduction reaction of Pt dispersed on boron doped graphene in acid medium.

PubMed

Pullamsetty, Ashok; Sundara, Ramaprabhu

2016-10-01

Boron doped graphene was prepared by a facile method and platinum (Pt) decoration over boron doped graphene was done in various chemical reduction methods such as sodium borohydride (NaBH4), polyol and modified polyol. X-ray diffraction analysis indicates that the synthesized catalyst particles are present in a nanocrystalline structure and transmission and scanning electron microscopy were employed to investigate the morphology and particle distribution. The electrochemical properties were investigated with the help of the rotating disk electrode (RDE) technique and cyclic voltammetry. The results show that the oxygen reduction reaction (ORR) takes place by a four-electron process. The kinetics of the ORR was evaluated using K-L and Tafel plots. The electrocatalyst obtained in modified polyol reduction method has shown the better catalytic activity compared to other two electrocatalysts. Copyright © 2016 Elsevier Inc. All rights reserved.

[Heart rate variability study based on a novel RdR RR Intervals Scatter Plot].

PubMed

Lu, Hongwei; Lu, Xiuyun; Wang, Chunfang; Hua, Youyuan; Tian, Jiajia; Liu, Shihai

2014-08-01

On the basis of Poincare scatter plot and first order difference scatter plot, a novel heart rate variability (HRV) analysis method based on scatter plots of RR intervals and first order difference of RR intervals (namely, RdR) was proposed. The abscissa of the RdR scatter plot, the x-axis, is RR intervals and the ordinate, y-axis, is the difference between successive RR intervals. The RdR scatter plot includes the information of RR intervals and the difference between successive RR intervals, which captures more HRV information. By RdR scatter plot analysis of some records of MIT-BIH arrhythmias database, we found that the scatter plot of uncoupled premature ventricular contraction (PVC), coupled ventricular bigeminy and ventricular trigeminy PVC had specific graphic characteristics. The RdR scatter plot method has higher detecting performance than the Poincare scatter plot method, and simpler and more intuitive than the first order difference method.

Evaluating the Aging of Multiple Emulsions Using Resonance-Enhanced Multiphoton Ionization Time-of-Flight Mass Spectrometry.

PubMed

Tsuda, Yukihiro; Uchimura, Tomohiro

2016-01-01

Resonance-enhanced multiphoton ionization time-of-flight mass spectrometry was applied to measurements of multiple emulsions with no pretreatment; a method for the quantitative evaluation of aging was proposed. We prepared water-in-oil-in-water (W/O/W) multiple emulsions containing toluene and m-phenylenediamine. The samples were measured immediately following both preparation and after having been stirred for 24 h. Time profiles of the peak areas for each analyte species were obtained, and several intense spikes for toluene could be detected from each sample after stirring, which suggests that the concentration of toluene in the middle phase had increased during stirring. On the other hand, in the case of a W/O/W multiple emulsion containing phenol and m-phenylenediamine, spikes for m-phenylenediamine, rather than phenol, were detected after stirring. In the present study, the time-profile data were converted into a scatter plot in order to quantitatively evaluate the aging. As a result, the ratio of the plots where strong signal intensities of toluene were detected increased from 8.4% before stirring to 33.2% after stirring for 24 h. The present method could be a powerful tool for evaluating multiple emulsions, such as studies on the kinetics of the encapsulation and release of active ingredients.

Development of a Novel Method for in vivo Determination of Activation Energy of Glucose Transport Across S. cerevisiae Cellular Membranes. A Biosensor-like Approach.

PubMed

Kormes, Diego J; Cortón, Eduardo

2009-01-01

Whereas biosensors have been usually proposed as analytical tools, used to investigate the surrounding media pursuing an analytical answer, we have used a biosensor-like device to characterize the microbial cells immobilized on it. We have studied the kinetics of transport and degradation of glucose at different concentrations and temperatures. When glucose concentrations of 15 and 1.5 mM were assayed, calculated activation energies were 25.2 and 18.4 kcal mol(-1), respectively, in good agreement with previously published data. The opportunity and convenience of using Arrhenius plots to estimate the activation energy in metabolic-related processes is also discussed.

Cross enyne metathesis of para-substituted styrenes: a kinetic study of enyne metathesis.

PubMed

Giessert, Anthony J; Diver, Steven T

2005-01-20

[Reaction: see text] The intermolecular enyne metathesis between alkynes and styrene derivatives was developed to study electronic effects in enyne metathesis. A Hammett plot for the overall reaction, catalyst initiation and vinyl carbene turnover was determined with the second generation Grubbs ruthenium carbene catalyst.

Analysis of atmospheric flow over a surface protrusion using the turbulence kinetic energy equation

NASA Technical Reports Server (NTRS)

Frost, W.; Harper, W. L.; Fichtl, G. H.

1975-01-01

Atmospheric flow fields resulting from a semi-elliptical surface obstruction in an otherwise horizontally homogeneous statistically stationary flow are modelled with the boundary-layer/Boussinesq-approximation of the governing equation of fluid mechanics. The turbulence kinetic energy equation is used to determine the dissipative effects of turbulent shear on the mean flow. Mean-flow results are compared with those given in a previous paper where the same problem was attacked using a Prandtl mixing-length hypothesis. Iso-lines of turbulence kinetic energy and turbulence intensity are plotted in the plane of the flow. They highlight regions of high turbulence intensity in the stagnation zone and sharp gradients in intensity along the transition from adverse to favourable pressure gradient.

Pharmaceutical quality of "party pills" raises additional safety concerns in the use of illicit recreational drugs.

PubMed

Young, Simon A; Thrimawithana, Thilini R; Antia, Ushtana; Fredatovich, John D; Na, Yonky; Neale, Peter T; Roberts, Amy F; Zhou, Huanyi; Russell, Bruce

2013-06-14

To determine the content and release kinetics of 1-benzylpiperazine (BZP) and 1-(3-trifluoromethyl-phenyl)piperazine (TFMPP) from "party pill" formulations. From these data, the possible impact of pharmaceutical quality upon the safety of such illicit formulations may be inferred. The amount of BZP and TFMPP in party pill formulations was determined using a validated HPLC method. The in-vitro release kinetics of selected party pill brands were determined using a USP dissolution apparatus (75 rpm, 37.5 degrees Celsius). The release data were then fitted to a first order release model using PLOT software and the time taken to achieve 90% release reported. Many of the tested party pill brands contained amounts of BZP and TFMPP that varied considerably from that stated on the packaging; including considerable TFMPP content in some brands not labelled to contain this drug. Dissolution studies revealed that there was considerable variability in the release kinetics between brands; in one case 90% release required >30 minutes. Lack of quality control in party pill manufacture may have led to the toxic effects reported by users unaware of the true content and release of drug from pills. More stringent regulation in the manufacture and quality control of "new generation party pills" is essential to the harm reduction campaign.

A critical analysis of the accuracy of several numerical techniques for combustion kinetic rate equations

NASA Technical Reports Server (NTRS)

Radhadrishnan, Krishnan

1993-01-01

A detailed analysis of the accuracy of several techniques recently developed for integrating stiff ordinary differential equations is presented. The techniques include two general-purpose codes EPISODE and LSODE developed for an arbitrary system of ordinary differential equations, and three specialized codes CHEMEQ, CREK1D, and GCKP4 developed specifically to solve chemical kinetic rate equations. The accuracy study is made by application of these codes to two practical combustion kinetics problems. Both problems describe adiabatic, homogeneous, gas-phase chemical reactions at constant pressure, and include all three combustion regimes: induction, heat release, and equilibration. To illustrate the error variation in the different combustion regimes the species are divided into three types (reactants, intermediates, and products), and error versus time plots are presented for each species type and the temperature. These plots show that CHEMEQ is the most accurate code during induction and early heat release. During late heat release and equilibration, however, the other codes are more accurate. A single global quantity, a mean integrated root-mean-square error, that measures the average error incurred in solving the complete problem is used to compare the accuracy of the codes. Among the codes examined, LSODE is the most accurate for solving chemical kinetics problems. It is also the most efficient code, in the sense that it requires the least computational work to attain a specified accuracy level. An important finding is that use of the algebraic enthalpy conservation equation to compute the temperature can be more accurate and efficient than integrating the temperature differential equation.

Kinetic profile of amyloid formation in the presence of an aromatic inhibitor by nuclear magnetic resonance.

PubMed

Liu, Gai; Gaines, Jennifer C; Robbins, Kevin J; Lazo, Noel D

2012-10-11

The self-assembly of amyloid proteins into β-sheet rich assemblies is associated with human amyloidoses including Alzheimer's disease, Parkinson's disease, and type 2 diabetes. An attractive therapeutic strategy therefore is to develop small molecules that would inhibit protein self-assembly. Natural polyphenols are potential inhibitors of β-sheet formation. How these compounds affect the kinetics of self-assembly studied by thioflavin T (ThT) fluorescence is not understood primarily because their presence interferes with ThT fluorescence. Here, we show that by plotting peak intensities from nuclear magnetic resonance (NMR) against incubation time, kinetic profiles in the presence of the polyphenol can be obtained from which kinetic parameters of self-assembly can be easily determined. In applying this technique to the self-assembly of the islet amyloid polypeptide in the presence of curcumin, a biphenolic compound found in turmeric, we show that the kinetic profile is atypical in that it shows a prenucleation period during which there is no observable decrease in NMR peak intensities.

Optimal design of a plot cluster for monitoring

Treesearch

Charles T. Scott

1993-01-01

Traveling costs incurred during extensive forest surveys make cluster sampling cost-effective. Clusters are specified by the type of plots, plot size, number of plots, and the distance between plots within the cluster. A method to determine the optimal cluster design when different plot types are used for different forest resource attributes is described. The method...

Use of mushroom tyrosinase to introduce michaelis-menten enzyme kinetics to biochemistry students.

PubMed

Flurkey, William H; Inlow, Jennifer K

2017-05-01

An inexpensive enzyme kinetics laboratory exercise for undergraduate biochemistry students is described utilizing tyrosinase from white button mushrooms. The exercise can be completed in one or two three-hour lab sessions. The optimal amounts of enzyme, substrate (catechol), and inhibitor (kojic acid) are first determined, and then kinetic data is collected in the absence and presence of the inhibitor. A Microsoft Excel template is used to plot the data and to fit the Michaelis-Menten equation to the data to determine the kinetic parameters V max and K m . The exercise is designed to clarify and reinforce concepts covered in an accompanying biochemistry lecture course. It has been used with positive results in an upper-level biochemistry laboratory course for junior/senior students majoring in chemistry or biology. © 2016 by The International Union of Biochemistry and Molecular Biology, 45(3):270-276, 2017. © 2016 The International Union of Biochemistry and Molecular Biology.

Microbial respiration and kinetics of extracellular enzymes activities through rhizosphere and detritusphere at agricultural site

NASA Astrophysics Data System (ADS)

Löppmann, Sebastian; Blagodatskaya, Evgenia; Kuzyakov, Yakov

2014-05-01

Rhizosphere and detritusphere are soil microsites with very high resource availability for microorganisms affecting their biomass, composition and functions. In the rhizosphere low molecular compounds occur with root exudates and low available polymeric compounds, as belowground plant senescence. In detritusphere the substrate for decomposition is mainly a polymeric material of low availability. We hypothesized that microorganisms adapted to contrasting quality and availability of substrates in the rhizosphere and detritusphere are strongly different in affinity of hydrolytic enzymes responsible for decomposition of organic compounds. According to common ecological principles easily available substrates are quickly consumed by microorganisms with enzymes of low substrate affinity (i.e. r-strategists). The slow-growing K-strategists with enzymes of high substrate affinity are better adapted for growth on substrates of low availability. Estimation of affinity of enzyme systems to the substrate is based on Michaelis-Menten kinetics, reflecting the dependency of decomposition rates on substrate amount. As enzymes-mediated reactions are substrate-dependent, we further hypothesized that the largest differences in hydrolytic activity between the rhizosphere and detritusphere occur at substrate saturation and that these differences are smoothed with increasing limitation of substrate. Affected by substrate limitation, microbial species follow a certain adaptation strategy. To achieve different depth gradients of substrate availability 12 plots on an agricultural field were established in the north-west of Göttingen, Germany: 1) 4 plots planted with maize, reflecting lower substrate availability with depth; 2) 4 unplanted plots with maize litter input (0.8 kg m-2 dry maize residues), corresponding to detritusphere; 3) 4 bare fallow plots as control. Maize litter was grubbed homogenously into the soil at the first 5 cm to ensure comparable conditions for the herbivore and detritivore communities in the soil. The kinetics (Km and Vmax) of four extracellular hydrolytic enzymes responsible for C- and phosphorous-cycle (β-glucosidase, β-xylosidase, β-cellobiohydrolase and acid phosphatase), microbial biomass, basal respiration (BR) and substrate-induced respiration (SIR) were measured in rhizosphere, detritusphere and control from 0 - 10 and 10 - 20 cm. The metabolic quotient (qCO2) was calculated as specific indicator for efficiency of microbial substrate utilization. We observed clear differences in enzymes activities at low and high concentrations of substrate. At substrate saturation enzyme activity rates of were significantly higher in rooted plots compared to litter amended plots, whereas at lower concentration no treatment effect could be found. The BR, SIR and qCO2 values were significantly higher at 0 - 10 cm of the planted treatment compared to litter and control plots, revealing a significantly higher respiration at lower efficiency of microbial substrate utilization in the rhizosphere. The Michaelis-Menten constant (Km) decreased with depth, especially for β-glucosidase, acid phosphatase and β-xylosidase, indicating higher substrate affinity of microorganisms in deeper soil and therefore different enzyme systems functioning. The substrate affinity factor (Vmax/Km) increased 2-fold with depth for various enzymes, reflecting a switch of predominantly occurring microbial strategies. Vmax/Km ratio indicated relative domination of zymogenous microbial communities (r-strategists) in 0 - 10 cm depth as compared with 10 - 20 cm depth where the K-strategists dominated.

Bioaccumulation of organic contaminants by benthic invertebrates of the Chesapeake Bay

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

Kimbrough, K.; Dickhut, R.

1995-12-31

In situ partitioning of PCBs and PAHs between benthic invertebrates and the environment has been compared to previously obtained laboratory bioaccumulation results. Previous laboratory studies show a characteristic nonlinear plot when bioaccumulation factors (BAF) are plotted against octanol-water partition coefficients (K{sub ow}), on a log-log scale. This phenomena can be explained by desorption and elimination kinetics. However preliminary in situ studies show a different relationship between field BAFs and K{sub ow} which may be explained by other biogeochemical factors. In situ and laboratory PAH and PCB partitioning measurements will be used to determine major mechanisms affecting contaminant bioaccumulation.

Methods for studying reaction kinetics in gas chromatography, exemplified by using the 1-chloro-2,2-dimethylaziridine interconversion reaction.

PubMed

Krupcík, J; Mydlová, J; Májek, P; Simon, P; Armstrong, D W

2008-04-04

In this paper, methods are described that are used for studying first-order reaction kinetics by gas chromatography. Basic theory is summarized and illustrated using the interconversion of 1-chloro-2,2-dimethylaziridine enantiomers as a representative example. For the determination of the kinetic and thermodynamic activation data of interconversion the following methods are reviewed: (i) classical kinetic methods where samples of batch-wise kinetic studies are analyzed by enantioselective gas chromatography, (ii) stopped-flow methods performed on one chiral column, (iii) stopped-flow methods performed on an achiral column or empty capillary coupled in series with two chiral columns, (iv) on-flow method performed on an achiral column coupled in series with two chiral columns, and (v) reaction gas chromatography, known as a dynamic gas chromatography, where the interconversion is performed on chiral column during the separation process. The determination of kinetic and thermodynamic activation data by methods (i) through (iv) is straightforward as the experimental data needed for the evaluation (particularly the concentration of reaction constituents) are accessible from the chromatograms. The evaluation of experiments from reaction chromatography method (v) is complex as the concentration bands of reaction constituents are overlapped. The following procedures have been developed to determination peak areas of reaction constituents in such complex chromatograms: (i) methods based on computer-assisted simulations of chromatograms where the kinetic activation parameters for the interconversion of enantiomers are obtained by iterative comparison of experimental and simulated chromatograms, (ii) stochastic methods based on the simulation of Gaussian distribution functions and using a time-dependent probability density function, (iii) approximation function and unified equation, (iv) computer-assisted peak deconvolution methods. Evaluation of the experimental data permits the calculation of apparent rate constants for both the interconversion of the first eluted (k (A-->B)(app)) as well as the second eluted (k(B-->A)(app)) enantiomer. The mean value for all the rate constants (from all the reviewed methods) was found for 1-chloro-2,2-dimethylaziridine A-->B enantiomer interconversion at 100 degrees C: k (A-->B)(app)=21.2 x 10(-4)s(-1) with a standard deviation sigma=10.7 x 10(-4). Evaluating data for reaction chromatography at 100 degrees C {k (app)=k(A-->B)(app)=k(B-->A)(app)=13.9 x 10(-4)s(-1), sigma=3.0 x 10(-4)s(-1)} shows that differences between k(A-->B)(app) and k(B-->A)(app) are the same within experimental error. It was shown both theoretically and experimentally that the Arrhenius activation energy (E(a)) calculated from Arrhenius plots (lnk(app) versus 1/T) is proportional to the enthalpy of activation {E(a)=DeltaH+RT}. Statistical treatment of Gibbs activation energy values gave: DeltaG (app)=110.5kJmol(-1), sigma=2.4kJmol(-1), DeltaG (A-->B)(app)=110.5kJmol(-1), sigma=2.2kJmol(-1), DeltaG (B-->A)(app)=110.3kJmol(-1), sigma=2.8kJmol(-1). This shows that the apparent Gibbs energy barriers for the interconversion of 1-chloro-2,2-dimethylaziridine enantiomers are equal DeltaG (app)=DeltaG(A-->B)(app)=DeltaG(B-->A)(app) and within the given precision of measurement independent of the experimental method used.

Application of Hill's equation for estimating area under the concentration-time curve (AUC) and use of time to AUC 90% for expressing kinetics of drug disposition.

PubMed

Cheng, Hsien C

2009-01-01

Half life and its derived pharmacokinetic parameters are calculated on an assumption that the terminal phase of drug disposition follows a constant rate of disposition. In reality, this assumption may not necessarily be the case. A new method is needed for analyzing PK parameters if the disposition does not follow a first order PK kinetic. Cumulative area under the concentration-time curve (AUC) is plotted against time to yield a hyperbolic (or sigmoidal) AUC-time relationship curve which is then analyzed by Hill's equation to yield AUC(inf), time to achieving AUC50% (T(AUC50%)) or AUC90% (T(AUC90%)), and the Hill's slope. From these parameters, an AUC-time relationship curve can be reconstructed. Projected plasma concentration can be calculated for any time point. Time at which cumulative AUC reaches 90% (T(AUC90%)) can be used as an indicator for expressing how fast a drug is cleared. Clearance is calculated in a traditional manner (i.v. dose/AUC(inf)), and the volume of distribution is proposed to be calculated at T(AUC50%) (0.5 i.v. dose/plasma concentration at T(AUC50%)). This method of estimating AUC is applicable for both i.v. and oral data. It is concluded that the Hill's equation can be used as an alternative method for estimating AUC and analysis of PK parameters if the disposition does not follow a first order kinetic. T(AUC90%) is proposed to be used as an indicator for expressing how fast a drug is cleared from the system.

Dynamic contrast-enhanced CT of head and neck tumors: perfusion measurements using a distributed-parameter tracer kinetic model. Initial results and comparison with deconvolution-based analysis

NASA Astrophysics Data System (ADS)

Bisdas, Sotirios; Konstantinou, George N.; Sherng Lee, Puor; Thng, Choon Hua; Wagenblast, Jens; Baghi, Mehran; San Koh, Tong

2007-10-01

The objective of this work was to evaluate the feasibility of a two-compartment distributed-parameter (DP) tracer kinetic model to generate functional images of several physiologic parameters from dynamic contrast-enhanced CT data obtained of patients with extracranial head and neck tumors and to compare the DP functional images to those obtained by deconvolution-based DCE-CT data analysis. We performed post-processing of DCE-CT studies, obtained from 15 patients with benign and malignant head and neck cancer. We introduced a DP model of the impulse residue function for a capillary-tissue exchange unit, which accounts for the processes of convective transport and capillary-tissue exchange. The calculated parametric maps represented blood flow (F), intravascular blood volume (v1), extravascular extracellular blood volume (v2), vascular transit time (t1), permeability-surface area product (PS), transfer ratios k12 and k21, and the fraction of extracted tracer (E). Based on the same regions of interest (ROI) analysis, we calculated the tumor blood flow (BF), blood volume (BV) and mean transit time (MTT) by using a modified deconvolution-based analysis taking into account the extravasation of the contrast agent for PS imaging. We compared the corresponding values by using Bland-Altman plot analysis. We outlined 73 ROIs including tumor sites, lymph nodes and normal tissue. The Bland-Altman plot analysis revealed that the two methods showed an accepted degree of agreement for blood flow, and, thus, can be used interchangeably for measuring this parameter. Slightly worse agreement was observed between v1 in the DP model and BV but even here the two tracer kinetic analyses can be used interchangeably. Under consideration of whether both techniques may be used interchangeably was the case of t1 and MTT, as well as for measurements of the PS values. The application of the proposed DP model is feasible in the clinical routine and it can be used interchangeably for measuring blood flow and vascular volume with the commercially available reference standard of the deconvolution-based approach. The lack of substantial agreement between the measurements of vascular transit time and permeability-surface area product may be attributed to the different tracer kinetic principles employed by both models and the detailed capillary tissue exchange physiological modeling of the DP technique.

Measurement techniques for analysis of fission fragment excited gases

NASA Technical Reports Server (NTRS)

Schneider, R. T.; Carroll, E. E.; Davis, J. F.; Davie, R. N.; Maguire, T. C.; Shipman, R. G.

1976-01-01

Spectroscopic analysis of fission fragment excited He, Ar, Xe, N2, Ne, Ar-N2, and Ne-N2 have been conducted. Boltzmann plot analysis of He, Ar and Xe have indicated a nonequilibrium, recombining plasma, and population inversions have been found in these gases. The observed radiating species in helium have been adequately described by a simple kinetic model. A more extensive model for argon, nitrogen and Ar-N2 mixtures was developed which adequately describes the energy flow in the system and compares favorably with experimental measurements. The kinetic processes involved in these systems are discussed.

Convex Arrhenius plots and their interpretation

PubMed Central

Truhlar, Donald G.; Kohen, Amnon

2001-01-01

This paper draws attention to selected experiments on enzyme-catalyzed reactions that show convex Arrhenius plots, which are very rare, and points out that Tolman's interpretation of the activation energy places a fundamental model-independent constraint on any detailed explanation of these reactions. The analysis presented here shows that in such systems, the rate coefficient as a function of energy is not just increasing more slowly than expected, it is actually decreasing. This interpretation of the data provides a constraint on proposed microscopic models, i.e., it requires that any successful model of a reaction with a convex Arrhenius plot should be consistent with the microcanonical rate coefficient being a decreasing function of energy. The implications and limitations of this analysis to interpreting enzyme mechanisms are discussed. This model-independent conclusion has broad applicability to all fields of kinetics, and we also draw attention to an analogy with diffusion in metastable fluids and glasses. PMID:11158559

Phi-value analysis of apo-azurin folding: comparison between experiment and theory.

PubMed

Zong, Chenghang; Wilson, Corey J; Shen, Tongye; Wolynes, Peter G; Wittung-Stafshede, Pernilla

2006-05-23

Pseudomonas aeruginosa azurin is a 128-residue beta-sandwich metalloprotein; in vitro kinetic experiments have shown that it folds in a two-state reaction. Here, we used a variational free energy functional to calculate the characteristics of the transition state ensemble (TSE) for folding of the apo-form of P. aeruginosa azurin and investigate how it responds to thermal and mutational changes. The variational method directly yields predicted chevron plots for wild-type and mutant apo-forms of azurin. In parallel, we performed in vitro kinetic-folding experiments on the same set of azurin variants using chemical perturbation. Like the wild-type protein, all apo-variants fold in apparent two-state reactions both in calculations and in stopped-flow mixing experiments. Comparisons of phi (phi) values determined from the experimental and theoretical chevron parameters reveal an excellent agreement for most positions, indicating a polarized, highly structured TSE for folding of P. aeruginosa apo-azurin. We also demonstrate that careful analysis of side-chain interactions is necessary for appropriate theoretical description of core mutants.

Investigation of the hydrochlorination of SiCl4

NASA Technical Reports Server (NTRS)

Mui, J. Y. P.

1982-01-01

The hyrochlorination of SiC14 and m.g. silicon metal to produce SiHC13, was investigated. Reaction kinetic measurements were carried out to collect additional rate data at 525 C and 550 C. A theoretical study was carried out to provide a kinetic model and a rate equation for the hydrochlorination reaction. Results of this preliminary study show that the rate of formation of SiHC13 follows a pseudo first order kinetics. The rate constants were measured at three temperatures, 550 C, 500 C and 450 C, respectively. The activation energy was determined from the Arrhenius plot to give a value of 13.2 Kcal/mole. The design of a quartz reactor to measure reaction rates and equilibrium conversion of SiHC13 at reaction temperature up to 650 C was completed.

Saturation behavior: a general relationship described by a simple second-order differential equation.

PubMed

Kepner, Gordon R

2010-04-13

The numerous natural phenomena that exhibit saturation behavior, e.g., ligand binding and enzyme kinetics, have been approached, to date, via empirical and particular analyses. This paper presents a mechanism-free, and assumption-free, second-order differential equation, designed only to describe a typical relationship between the variables governing these phenomena. It develops a mathematical model for this relation, based solely on the analysis of the typical experimental data plot and its saturation characteristics. Its utility complements the traditional empirical approaches. For the general saturation curve, described in terms of its independent (x) and dependent (y) variables, a second-order differential equation is obtained that applies to any saturation phenomena. It shows that the driving factor for the basic saturation behavior is the probability of the interactive site being free, which is described quantitatively. Solving the equation relates the variables in terms of the two empirical constants common to all these phenomena, the initial slope of the data plot and the limiting value at saturation. A first-order differential equation for the slope emerged that led to the concept of the effective binding rate at the active site and its dependence on the calculable probability the interactive site is free. These results are illustrated using specific cases, including ligand binding and enzyme kinetics. This leads to a revised understanding of how to interpret the empirical constants, in terms of the variables pertinent to the phenomenon under study. The second-order differential equation revealed the basic underlying relations that describe these saturation phenomena, and the basic mathematical properties of the standard experimental data plot. It was shown how to integrate this differential equation, and define the common basic properties of these phenomena. The results regarding the importance of the slope and the new perspectives on the empirical constants governing the behavior of these phenomena led to an alternative perspective on saturation behavior kinetics. Their essential commonality was revealed by this analysis, based on the second-order differential equation.

Effects on run-off water quantity and quality of urban organic wastes applied in a degraded semi-arid ecosystem.

PubMed

Martínez, F; Casermeiro, M A; Morales, D; Cuevas, G; Walter, Ingrid

2003-04-15

Biosolids and composted municipal solid wastes were surface-applied (0 and 80 Mg ha(-1)) to a degraded soil in a semi-arid environment to determine their effects on the quantity and quality of run-off water. Three and 4 years after application, a simulated rainfall was performed (intensity=942.5 ml min(-1) and kinetic energy=3.92 J m(-2)) on 0.078 m(2) plots using a portable rainfall simulator. The run-off from the different treatment plots was collected and analysed. The type of treatment was highly related to infiltration, run-off and sediment production. The biosolid-treated plots showed the minimum value of total run-off, maximum time to the beginning of run-off and maximum run-off ratio (the relationship between total rainfall and run-off). The MSW-treated plots showed values intermediate between biosolid-treated plots and control plots. Soil losses were also closely related to treatment type. Control plots showed the maximum sediment yield, MSW-treated plots showed intermediate values, and biosolid plots the minimum values for washout. The concentrations of NH(4)-N and PO(4)-P in the run-off water were significantly higher in the treated plots than in control plots. The highest PO(4)-P value, 0.73 mg l(-1), was obtained in the soil treated with biosolids; NO(3)-N concentration also increased significantly with respect to the control and MSW treatments. NH(4)-N concentrations of 15.6 and 15.0 mg l(-1) were recorded in the soils treated with biosolids and MSW, respectively, values approximately five times higher than those obtained in run-off water from untreated soil. However, the concentrations of all these constituents were lower than threshold limits cited in water quality standards for agricultural use. With the exception of Cu, all trace metals analysed in the run-off water were below detection limits.

Tracer kinetics of forearm endothelial function: comparison of an empirical method and a quantitative modeling technique.

PubMed

Zhao, Xueli; Arsenault, Andre; Lavoie, Kim L; Meloche, Bernard; Bacon, Simon L

2007-01-01

Forearm Endothelial Function (FEF) is a marker that has been shown to discriminate patients with cardiovascular disease (CVD). FEF has been assessed using several parameters: the Rate of Uptake Ratio (RUR), EWUR (Elbow-to-Wrist Uptake Ratio) and EWRUR (Elbow-to-Wrist Relative Uptake Ratio). However, the modeling functions of FEF require more robust models. The present study was designed to compare an empirical method with quantitative modeling techniques to better estimate the physiological parameters and understand the complex dynamic processes. The fitted time activity curves of the forearms, estimating blood and muscle components, were assessed using both an empirical method and a two-compartment model. Although correlational analyses suggested a good correlation between the methods for RUR (r=.90) and EWUR (r=.79), but not EWRUR (r=.34), Altman-Bland plots found poor agreement between the methods for all 3 parameters. These results indicate that there is a large discrepancy between the empirical and computational method for FEF. Further work is needed to establish the physiological and mathematical validity of the 2 modeling methods.

A miniaturized fibrinolytic assay for plasminogen activators

NASA Technical Reports Server (NTRS)

Lewis, M. L.; Nachtwey, D. S.; Damron, K. L.

1991-01-01

This report describes a micro-clot lysis assay (MCLA) for evaluating fibrinolytic activity of plasminogen activators (PA). Fibrin clots were formed in wells of microtiter plates. Lysis of the clots by PA, indicated by change in turbidity (optical density, OD), was monitored with a microplate reader at five minutes intervals. Log-log plots of PA dilution versus endpoint, the time at which the OD value was halfway between the maximum and minimum value for each well, were linear over a broad range of PA concentrations (2-200 International units/ml). The MCLA is a modification and miniaturization of well established fibrinolytic methods. The significant practical advantages of the MCLA are that it is a simple, relatively sensitive, non-radioactive, quantitative, kinetic, fibrinolytic micro-technique which can be automated.

Development of a Novel Method for in vivo Determination of Activation Energy of Glucose Transport Across S. cerevisiae Cellular Membranes. A Biosensor-like Approach

PubMed Central

Kormes, Diego J.; Cortón, Eduardo

2009-01-01

Whereas biosensors have been usually proposed as analytical tools, used to investigate the surrounding media pursuing an analytical answer, we have used a biosensor-like device to characterize the microbial cells immobilized on it. We have studied the kinetics of transport and degradation of glucose at different concentrations and temperatures. When glucose concentrations of 15 and 1.5 mM were assayed, calculated activation energies were 25.2 and 18.4 kcal mol−1, respectively, in good agreement with previously published data. The opportunity and convenience of using Arrhenius plots to estimate the activation energy in metabolic-related processes is also discussed. PMID:22573975

Glycyrrhetinic acid exhibits strong inhibitory effects towards UDP-glucuronosyltransferase (UGT) 1A3 and 2B7.

PubMed

Huang, Yin-Peng; Cao, Yun-Feng; Fang, Zhong-Ze; Zhang, Yan-Yan; Hu, Cui-Min; Sun, Xiao-Yu; Yu, Zhen-Wen; Zhu, Xu; Hong, Mo; Yang, Lu; Sun, Hong-Zhi

2013-09-01

The aim of the present study is to evaluate the inhibitory effects of liver UDP-glucuronosyltransferases (UGTs) by glycyrrhizic acid and glycyrrhetinic acid, which are the bioactive ingredients isolated from licorice. The results showed that glycyrrhetinic acid exhibited stronger inhibition towards all the tested UGT isoforms, indicating that the deglycosylation process played an important role in the inhibitory potential towards UGT isoforms. Furthermore, the inhibition kinetic type and parameters were determined for the inhibition of glycyrrhetinic acid towards UGT1A3 and UGT2B7. Data fitting using Dixon and Lineweaver-Burk plots demonstrated that the inhibition of UGT1A3 and UGT2B7 by glycyrrhetinic acid was best fit to competitive and noncompetitive type, respectively. The second plot using the slopes from Lineweaver-Burk plots versus glycyrrhetinic acid concentrations was employed to calculate the inhibition kinetic parameters (K(i)), and the values were calculated to be 0.2 and 1.7 μM for UGT1A3 and UGT2B7, respectively. All these results remind us the possibility of UGT inhibition-based herb-drug interaction. However, the explanation of these in vitro parameters should be paid more caution due to complicated factors, including the probe substrate-dependent UGT inhibition behaviour, environmental factors affecting the abundance of herbs' ingredients, and individual difference of pharmacokinetic factors. Copyright © 2012 John Wiley & Sons, Ltd.

Derringer desirability and kinetic plot LC-column comparison approach for MS-compatible lipopeptide analysis.

PubMed

D'Hondt, Matthias; Verbeke, Frederick; Stalmans, Sofie; Gevaert, Bert; Wynendaele, Evelien; De Spiegeleer, Bart

2014-06-01

Lipopeptides are currently re-emerging as an interesting subgroup in the peptide research field, having historical applications as antibacterial and antifungal agents and new potential applications as antiviral, antitumor, immune-modulating and cell-penetrating compounds. However, due to their specific structure, chromatographic analysis often requires special buffer systems or the use of trifluoroacetic acid, limiting mass spectrometry detection. Therefore, we used a traditional aqueous/acetonitrile based gradient system, containing 0.1% (m/v) formic acid, to separate four pharmaceutically relevant lipopeptides (polymyxin B 1 , caspofungin, daptomycin and gramicidin A 1 ), which were selected based upon hierarchical cluster analysis (HCA) and principal component analysis (PCA). In total, the performance of four different C18 columns, including one UPLC column, were evaluated using two parallel approaches. First, a Derringer desirability function was used, whereby six single and multiple chromatographic response values were rescaled into one overall D -value per column. Using this approach, the YMC Pack Pro C18 column was ranked as the best column for general MS-compatible lipopeptide separation. Secondly, the kinetic plot approach was used to compare the different columns at different flow rate ranges. As the optimal kinetic column performance is obtained at its maximal pressure, the length elongation factor λ ( P max / P exp ) was used to transform the obtained experimental data (retention times and peak capacities) and construct kinetic performance limit (KPL) curves, allowing a direct visual and unbiased comparison of the selected columns, whereby the YMC Triart C18 UPLC and ACE C18 columns performed as best. Finally, differences in column performance and the (dis)advantages of both approaches are discussed.

Formation of a new crystalline form of anhydrous β-maltose by ethanol-mediated crystal transformation.

PubMed

Verhoeven, Nicolas; Neoh, Tze Loon; Ohashi, Tetsuya; Furuta, Takeshi; Kurozumi, Sayaka; Yoshii, Hidefumi

2012-04-01

β-Maltose monohydrate was transformed into an anhydrous form by ethanol-mediated method under several temperatures with agitation. A new stable anhydrous form of β-maltose (Mβ(s)) was obtained, as substantiated by the X-ray diffraction patterns. Mβ(s) obtained by this method presented a fine porous structure, resulting in greater specific surface area compared to those of β-maltose monohydrate and anhydrous β-maltose obtained by vacuum drying (Mβ(h)). The crystal transformation presumably consisted of two steps: dehydration reaction from the hydrous to amorphous forms and crystal formation from the amorphous forms to the noble anhydrous form. The kinetics of these reactions were determined by thermal analysis using Jander's equation and Arrhenius plots. The overall activation energies of the dehydration reaction and the formation of anhydrous maltose were evaluated to be 100 and 90 kJ/mol, respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

Organic Lecture Demonstrations of Common-Ion Effect, Ionizing Power of Solvents, and First-Order Reaction Kinetics.

ERIC Educational Resources Information Center

Danen, Wayne C.; Blecha, M. Therese, Sr.

1982-01-01

Background information and experimental procedures are provided for three lecture-demonstrations (involving hydrolysis of tetra-butyl chloride) illustrating: (1) common-ion or mass law effect; (2) effect of changing ionizing power of a solvent on a solvolysis reaction; and (3) collecting/plotting data to illustrate a first-order reaction.…

Predicting repeat protein folding kinetics from an experimentally determined folding energy landscape

PubMed Central

Street, Timothy O; Barrick, Doug

2009-01-01

The Notch ankyrin domain is a repeat protein whose folding has been characterized through equilibrium and kinetic measurements. In previous work, equilibrium folding free energies of truncated constructs were used to generate an experimentally determined folding energy landscape (Mello and Barrick, Proc Natl Acad Sci USA 2004;101:14102–14107). Here, this folding energy landscape is used to parameterize a kinetic model in which local transition probabilities between partly folded states are based on energy values from the landscape. The landscape-based model correctly predicts highly diverse experimentally determined folding kinetics of the Notch ankyrin domain and sequence variants. These predictions include monophasic folding and biphasic unfolding, curvature in the unfolding limb of the chevron plot, population of a transient unfolding intermediate, relative folding rates of 19 variants spanning three orders of magnitude, and a change in the folding pathway that results from C-terminal stabilization. These findings indicate that the folding pathway(s) of the Notch ankyrin domain are thermodynamically selected: the primary determinants of kinetic behavior can be simply deduced from the local stability of individual repeats. PMID:19177351

Kinetics and mechanism of permanganate oxidation of iota- and lambda-carrageenan polysaccharides as sulfated carbohydrates in acid perchlorate solutions.

PubMed

Hassan, Refat M; Fawzy, Ahmed; Ahmed, Gamal A; Zaafarany, Ishaq A; Asghar, Basim H; Takagi, Hideo D; Ikeda, Yasuhisa

2011-10-18

The kinetics of oxidation of iota- and lambda-carrageenan as sulfated carbohydrates by permanganate ion in aqueous perchlorate solutions at a constant ionic strength of 2.0 mol dm(-3) have been investigated spectrophotometrically. The pseudo-first-order plots were found to be of inverted S-shape throughout the entire courses of reactions. The initial rates were found to be relatively slow in the early stages, followed by an increase in the oxidation rates over longer time periods. The experimental observations showed first-order dependences in permanganate and fractional first-order kinetics with respect to both carrageenans concentration for both the induction and autoacceleration periods. The results obtained at various hydrogen ion concentrations showed that the oxidation processes in these redox systems are acid-catalyzed throughout the two stages of oxidation reactions. The added salts lead to the prediction that Mn(III) is the reactive species throughout the autoacceleration periods. Kinetic evidence for the formation of 1:1 intermediate complexes was revealed. The kinetic parameters have been evaluated and tentative reaction mechanisms in good agreement with the kinetic results are discussed. Copyright © 2011 Elsevier Ltd. All rights reserved.

New Approach for Studying Slow Fragmentation Kinetics in FT-ICR: Surface-Induced Dissociation Combined with Resonant Ejection

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

Laskin, Julia; Futrell, Jean H.

2015-02-01

We introduce a new approach for studying the kinetics of large ion fragmentation in the gas phase by coupling surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer with resonant ejection of selected fragment ions using a relatively short (5 ms) ejection pulse. The approach is demonstrated for singly protonated angiotensin III ions excited by collisions with a self-assembled monolayer of alkylthiol on gold (HSAM). The overall decomposition rate and rate constants of individual reaction channels are controlled by varying the kinetic energy of the precursor ion in a range of 65–95 eV. The kinetics of peptidemore » fragmentation are probed by varying the delay time between resonant ejection and fragment ion detection at a constant total reaction time. RRKM modeling indicates that the shape of the kinetics plots is strongly affected by the shape and position of the energy deposition function (EDF) describing the internal energy distribution of the ion following ion-surface collision. Modeling of the kinetics data provides detailed information on the shape of the EDF and energy and entropy effects of individual reaction channels.« less

Measurement of Human Skeletal Muscle Oxidative Capacity by 31P-MRS: A Cross-Validation with in vitro measurements

PubMed Central

Lanza, Ian R.; Bhagra, Sumit; Nair, K. Sreekumaran; Port, John D.

2011-01-01

Purpose To cross-validate skeletal muscle oxidative capacity measured by 31P-MRS with in vitro measurements of oxidative capacityin mitochondria isolated from muscle biopsies of the same muscle group in 18 healthy adults. Materials and Methods Oxidative capacity in vivo was determined from PCr recovery kinetics following a 30s maximal isometric knee extension. State 3 respiration was measured in isolated mitochondria using high-resolution respirometry. A second cohort of 10 individuals underwent two 31P-MRS testing sessions to assess the test-retest reproducibility of the method. Results Overall, the in vivo and in vitro methods were well-correlated (r = 0.66 –0.72) and showed good agreement by Bland Altman plots. Excellent reproducibility was observed for the PCr recovery rate constant (CV = 4.6%, ICC = 0.85) and calculated oxidative capacity (CV = 3.4%, ICC = 0.83). Conclusion These results indicate that 31P-MRS corresponds well with gold-standard in vitro measurements and is highly reproducible. PMID:22006551

Visualizing the deep end of sound: plotting multi-parameter results from infrasound data analysis

NASA Astrophysics Data System (ADS)

Perttu, A. B.; Taisne, B.

2016-12-01

Infrasound is sound below the threshold of human hearing: approximately 20 Hz. The field of infrasound research, like other waveform based fields relies on several standard processing methods and data visualizations, including waveform plots and spectrograms. The installation of the International Monitoring System (IMS) global network of infrasound arrays, contributed to the resurgence of infrasound research. Array processing is an important method used in infrasound research, however, this method produces data sets with a large number of parameters, and requires innovative plotting techniques. The goal in designing new figures is to be able to present easily comprehendible, and information-rich plots by careful selection of data density and plotting methods.

A fast hidden line algorithm for plotting finite element models

NASA Technical Reports Server (NTRS)

Jones, G. K.

1982-01-01

Effective plotting of finite element models requires the use of fast hidden line plot techniques that provide interactive response. A high speed hidden line technique was developed to facilitate the plotting of NASTRAN finite element models. Based on testing using 14 different models, the new hidden line algorithm (JONES-D) appears to be very fast: its speed equals that for normal (all lines visible) plotting and when compared to other existing methods it appears to be substantially faster. It also appears to be very reliable: no plot errors were observed using the new method to plot NASTRAN models. The new algorithm was made part of the NPLOT NASTRAN plot package and was used by structural analysts for normal production tasks.

Reinterpretation of curved Hammett plots in reaction of nucleophiles with aryl benzoates: change in rate-determining step or mechanism versus ground-state stabilization.

PubMed

Um, Ik-Hwan; Han, Hyun-Joo; Ahn, Jung-Ae; Kang, Swan; Buncel, Erwin

2002-11-29

A kinetic study is reported for the reaction of the anionic nucleophiles OH-, CN-, and N 3 - with aryl benzoates containing substituents on the benzoyl as well as the aryloxy moiety, in 80 mol % H2O - 20 mol % dimethyl sulfoxide at 25.0 degrees C. Hammett log k vs sigma plots for these systems are consistently nonlinear. However, a possible traditional explanation in terms of a mechanism involving a tetrahedral intermediate with curvature resulting from a change in rate-determining step is considered but rejected. The proposed explanation involves ground-state stabilization through resonance interaction between the benzoyl substituent and the electrophilic carbonyl center in the two-stage mechanism. Accordingly, the data are nicely accommodated on the basis of the Yukawa-Tsuno equation, which gives linear plots for all three nuceophiles. Literature reports of the mechanism of acyl transfer processes are reconsidered in this light.

An eco-friendly stability-indicating spectrofluorimetric method for the determination of two anticancer stereoisomer drugs in their pharmaceutical preparations following micellar enhancement: Application to kinetic degradation studies.

PubMed

El-Kimary, Eman I; El-Yazbi, Amira F

2016-06-15

A new rapid and highly sensitive stability-indicating spectrofluorimetric method was developed for the determination of two stereoisomers anticancer drugs, doxorubicin (DOX) and epirubicin (EPI) in pure form and in pharmaceutical preparations. The fluorescence spectral behavior of DOX and EPI in a sodium dodecyl sulfate (SDS) micellar system was investigated. It was found that the fluorescence intensity of DOX and EPI in an aqueous solution of phosphate buffer pH4.0 and in the presence of SDS was greatly (about two fold) enhanced and the mechanism of fluorescence enhancement effect of SDS on DOX was also investigated. The fluorescence intensity of DOX or EPI was measured at 553nm after excitation at 497nm. The plots of fluorescence intensity versus concentration were rectilinear over a range of 0.03-2μg/mL for both DOX and EPI with good correlation coefficient (r>0.999). High sensitivity to DOX and EPI was attained using the proposed method with limits of detection of 10 and 9ng/mL and limits of quantitation of 29 and 28ng/mL, for DOX and EPI, respectively. The method was successfully applied for the determination of DOX and EPI in biological fluids and in their commercial pharmaceutical preparations and the results were concordant with those obtained using a previously reported method. The application of the proposed method was extended to stability studies of DOX following different forced degradation conditions (acidic, alkaline, oxidative and photolytic) according to ICH guidelines. Moreover, the kinetics of the alkaline and oxidative degradation of DOX was investigated and the apparent first-order rate constants and half-life times were calculated. Copyright © 2016 Elsevier B.V. All rights reserved.

Carbon-supported PdM (M = Au and Sn) nanocatalysts for the electrooxidation of ethanol in high pH media

NASA Astrophysics Data System (ADS)

He, Qinggang; Chen, Wei; Mukerjee, Sanjeev; Chen, Shaowei; Laufek, František

Carbon-supported Pd 4Au- and Pd 2.5Sn-alloyed nanoparticles were prepared by a chemical reduction method, and characterized by a wide array of experimental techniques including mass spectrometry, transmission electron microscopy, and X-ray diffraction spectroscopy. Ethanol electrooxidation on the as-synthesized catalysts and commercial Pt/C was then investigated and compared in alkaline media by cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy studies at room temperature. Voltammetric and chronoamperometric measurements showed higher current density and longer term stability in ethanol oxidation with the palladium alloy nanocatalysts than with the commercial one. Electrochemical impedance spectroscopy and Tafel plots were employed to examine the charge-transfer kinetics of ethanol electrooxidation. The results suggest that whereas the reaction kinetics might be somewhat more sluggish on the Pd-based alloy catalysts than on commercial Pt/C, the former appeared to have a higher tolerance to surface poisoning. Overall, the Pd-based alloy catalysts represent promising candidates for the electrocatalytic oxidation of ethanol, and Pd 4Au/C displays the best catalytic activity among the series for the ethanol oxidation in alkaline media.

Pyrolysis and kinetic analyses of a perennial grass (Saccharum ravannae L.) from north-east India: Optimization through response surface methodology and product characterization.

PubMed

Saikia, Ruprekha; Baruah, Bhargav; Kalita, Dipankar; Pant, Kamal K; Gogoi, Nirmali; Kataki, Rupam

2018-04-01

The objective of the present investigation was to optimize the pyrolysis condition of an abundantly available and low cost perennial grass of north-east India Saccharum ravannae L. (S. ravannae) using response surface methodology based on central composite design. Kinetic study of the biomass was conducted at four different heating rates of 10, 20, 40 and 60 °C min -1 and results were interpreted by Friedman, Kissinger Akira Sunnose and Flynn-Wall-Ozawa methods. Average activation energy 151.45 kJ mol -1 was used for evaluation of reaction mechanism following Criado master plot. Maximum bio-oil yield of 38.1 wt% was obtained at pyrolysis temperature of 550 °C, heating rate of 20 °C min -1 and nitrogen flow rate of 226 mL min -1 . Study on bio-oil quality revealed higher content of hydrocarbon, antioxidant property, total phenolic content and metal chelating capacity. These opened up probable applications of S. ravannae bio-oil in different fields including fuel, food industry and biomedical domain. Copyright © 2018 Elsevier Ltd. All rights reserved.

Maintaining a permanent plot data base for growth and yield research: Solutions to some recurring problems

Treesearch

John C. Byrne

1993-01-01

Methods for solving some recurring problems of maintaining a permanent plot data base for growth and yield reseuch are described. These methods include documenting data from diverse sampling designs, changing sampling designs, changing field procedures, and coordinating activities in the plots with the land management agency. Managing a permanent plot data base (...

Possibility of using NURBS for surface plotting by survey data

NASA Astrophysics Data System (ADS)

Pravdina, E. A.; Lepikhina, O. J.

2018-05-01

Different methods of surface plotting were discussed in this article. Constructing the surface with the help of the Delaunay triangulation algorithm is described. The TIN-surfaces (triangles irregular net) method is used in the entire CAD software. This type of surfaces is plotting by results of laser scanning and stadia surveying. Possibility of using spline surfaces (NURBS) for surface plotting is studied. For a defined number of points by Mathcad software, the curvilinear function that described two-dimensional spline surfaces was calculated and plotted.

Graphical Data Analysis on the Circle: Wrap-Around Time Series Plots for (Interrupted) Time Series Designs.

PubMed

Rodgers, Joseph Lee; Beasley, William Howard; Schuelke, Matthew

2014-01-01

Many data structures, particularly time series data, are naturally seasonal, cyclical, or otherwise circular. Past graphical methods for time series have focused on linear plots. In this article, we move graphical analysis onto the circle. We focus on 2 particular methods, one old and one new. Rose diagrams are circular histograms and can be produced in several different forms using the RRose software system. In addition, we propose, develop, illustrate, and provide software support for a new circular graphical method, called Wrap-Around Time Series Plots (WATS Plots), which is a graphical method useful to support time series analyses in general but in particular in relation to interrupted time series designs. We illustrate the use of WATS Plots with an interrupted time series design evaluating the effect of the Oklahoma City bombing on birthrates in Oklahoma County during the 10 years surrounding the bombing of the Murrah Building in Oklahoma City. We compare WATS Plots with linear time series representations and overlay them with smoothing and error bands. Each method is shown to have advantages in relation to the other; in our example, the WATS Plots more clearly show the existence and effect size of the fertility differential.

Interactive computer methods for generating mineral-resource maps

USGS Publications Warehouse

Calkins, James Alfred; Crosby, A.S.; Huffman, T.E.; Clark, A.L.; Mason, G.T.; Bascle, R.J.

1980-01-01

Inasmuch as maps are a basic tool of geologists, the U.S. Geological Survey's CRIB (Computerized Resources Information Bank) was constructed so that the data it contains can be used to generate mineral-resource maps. However, by the standard methods used-batch processing and off-line plotting-the production of a finished map commonly takes 2-3 weeks. To produce computer-generated maps more rapidly, cheaply, and easily, and also to provide an effective demonstration tool, we have devised two related methods for plotting maps as alternatives to conventional batch methods. These methods are: 1. Quick-Plot, an interactive program whose output appears on a CRT (cathode-ray-tube) device, and 2. The Interactive CAM (Cartographic Automatic Mapping system), which combines batch and interactive runs. The output of the Interactive CAM system is final compilation (not camera-ready) paper copy. Both methods are designed to use data from the CRIB file in conjunction with a map-plotting program. Quick-Plot retrieves a user-selected subset of data from the CRIB file, immediately produces an image of the desired area on a CRT device, and plots data points according to a limited set of user-selected symbols. This method is useful for immediate evaluation of the map and for demonstrating how trial maps can be made quickly. The Interactive CAM system links the output of an interactive CRIB retrieval to a modified version of the CAM program, which runs in the batch mode and stores plotting instructions on a disk, rather than on a tape. The disk can be accessed by a CRT, and, thus, the user can view and evaluate the map output on a CRT immediately after a batch run, without waiting 1-3 days for an off-line plot. The user can, therefore, do most of the layout and design work in a relatively short time by use of the CRT, before generating a plot tape and having the map plotted on an off-line plotter.

Tracking Changes in Cardiac Output: Statistical Considerations on the 4-Quadrant Plot and the Polar Plot Methodology.

PubMed

Saugel, Bernd; Grothe, Oliver; Wagner, Julia Y

2015-08-01

When comparing 2 technologies for measuring hemodynamic parameters with regard to their ability to track changes, 2 graphical tools are omnipresent in the literature: the 4-quadrant plot and the polar plot recently proposed by Critchley et al. The polar plot is thought to be the more advanced statistical tool, but care should be taken when it comes to its interpretation. The polar plot excludes possibly important measurements from the data. The polar plot transforms the data nonlinearily, which may prevent it from being seen clearly. In this article, we compare the 4-quadrant and the polar plot in detail and thoroughly describe advantages and limitations of each. We also discuss pitfalls concerning the methods to prepare the researcher for the sound use of both methods. Finally, we briefly revisit the Bland-Altman plot for the use in this context.

Real-time cytometric assay of nitric oxide and superoxide interaction in peripheral blood monocytes: A no-wash, no-lyse kinetic method.

PubMed

Balaguer, Susana; Diaz, Laura; Gomes, Angela; Herrera, Guadalupe; O'Connor, José-Enrique; Urios, Amparo; Felipo, Vicente; Montoliu, Carmina

2017-05-01

Nitric oxide (NO) and its related reactive nitrogen species (RNS) and reactive oxygen species (ROS) are crucial in monocyte responses against pathogens and also in inflammatory conditions. Central to both processes is the generation of the strong oxidant peroxynitrite (ONOO) by a fast reaction between NO and superoxide anion. ONOO is a biochemical junction for ROS- and RNS cytotoxicity and causes protein nitrosylation. Circulating by-products of protein nitrosylation are early biomarkers of inflammation-based conditions, including minimal hepatic encephalopathy in cirrhotic patients (Montoliu et al., Am J Gastroenterol 2011; 106:1629-1637). In this context, we have designed a novel no-wash, no-lyse real-time flow cytometry assay to detect and follow-up the NO- and superoxide-driven generation of ONOO in peripheral blood monocytes. Whole blood samples were stained with CD45 and CD14 antibodies plus one of a series of fluorescent probes sensitive to RNS, ROS, or glutathione, namely 4-amino-5-methylamino-2',7'-difluorofluorescein diacetate, dihydrorhodamine 123, MitoSOX Red, dihydroethidium, and 5-chloromethylfluorescein diacetate. Samples were exposed sequentially to a NO donor and three different superoxide donors, and analyzed in real time by kinetic flow cytometry. Relevant kinetic descriptors, such as the rate of fluorescence change, were calculated from the kinetic plot. The generation of ONOO, which consumes both NO and superoxide, led to a decrease in the intensity of the cellular fluorescence of the probes sensitive to these molecules. This is a fast and simple assay that may be used to monitor the intracellular generation of ONOO in physiological, pathological, and pharmacological contexts. © 2015 International Clinical Cytometry Society. © 2015 International Clinical Cytometry Society.

Uncovering Oscillations, Complexity, and Chaos in Chemical Kinetics Using Mathematica

NASA Astrophysics Data System (ADS)

Ferreira, M. M. C.; Ferreira, W. C., Jr.; Lino, A. C. S.; Porto, M. E. G.

1999-06-01

Unlike reactions with no peculiar temporal behavior, in oscillatory reactions concentrations can rise and fall spontaneously in a cyclic or disorganized fashion. In this article, the software Mathematica is used for a theoretical study of kinetic mechanisms of oscillating and chaotic reactions. A first simple example is introduced through a three-step reaction, called the Lotka model, which exhibits a temporal behavior characterized by damped oscillations. The phase plane method of dynamic systems theory is introduced for a geometric interpretation of the reaction kinetics without solving the differential rate equations. The equations are later numerically solved using the built-in routine NDSolve and the results are plotted. The next example, still with a very simple mechanism, is the Lotka-Volterra model reaction, which oscillates indefinitely. The kinetic process and rate equations are also represented by a three-step reaction mechanism. The most important difference between this and the former reaction is that the undamped oscillation has two autocatalytic steps instead of one. The periods of oscillations are obtained by using the discrete Fourier transform (DFT)-a well-known tool in spectroscopy, although not so common in this context. In the last section, it is shown how a simple model of biochemical interactions can be useful to understand the complex behavior of important biological systems. The model consists of two allosteric enzymes coupled in series and activated by its own products. This reaction scheme is important for explaining many metabolic mechanisms, such as the glycolytic oscillations in muscles, yeast glycolysis, and the periodic synthesis of cyclic AMP. A few of many possible dynamic behaviors are exemplified through a prototype glycolytic enzymatic reaction proposed by Decroly and Goldbeter. By simply modifying the initial concentrations, limit cycles, chaos, and birhythmicity are computationally obtained and visualized.

Rapid Detection of Microbial Contamination Using a Microfluidic Device.

PubMed

Al-Adhami, Mustafa; Tilahun, Dagmawi; Rao, Govind; Gurramkonda, Chandrasekhar; Kostov, Yordan

2017-01-01

A portable kinetics fluorometer is developed to detect viable cells which may be contaminating various samples. The portable device acts as a single-excitation, single-emission photometer that continuously measures fluorescence intensity of an indicator dye and plots it. The slope of the plot depends on the number of colony forming units per milliliter. The device uses resazurin as the indicator dye. Viable cells reduce resazurin to resorufin, which is more fluorescent. Photodiode is used to detect fluorescence change. The photodiode generated current proportional to the intensity of the light that reached it, and an op-amp is used in a transimpedance differential configuration to ensure amplification of the photodiode's signal. A microfluidic chip is designed specifically for the device. It acts as a fully enclosed cuvette, which enhances the resazurin reduction rate. In tests, the E. coli-containing media are injected into the microfluidic chip and the device is able to detect the presence of E. coli in LB media based on the fluorescence change that occurred in the indicator dye. The device provides fast, accurate, and inexpensive means to optical detection of the presence of viable cells and could be used in the field in place of more complex methods, i.e., loop-meditated isothermal amplification of DNA (LAMP) to detect bacteria in pharmaceutical samples (Jimenez et al., J Microbiol Methods 41(3):259-265, 2000) or measuring the intrinsic fluorescence of the bacterial or yeast chromophores (Estes et al., Biosens Bioelectron 18(5):511-519, 2003).

A quasi-chemical model for the growth and death of microorganisms in foods by non-thermal and high-pressure processing.

PubMed

Doona, Christopher J; Feeherry, Florence E; Ross, Edward W

2005-04-15

Predictive microbial models generally rely on the growth of bacteria in laboratory broth to approximate the microbial growth kinetics expected to take place in actual foods under identical environmental conditions. Sigmoidal functions such as the Gompertz or logistics equation accurately model the typical microbial growth curve from the lag to the stationary phase and provide the mathematical basis for estimating parameters such as the maximum growth rate (MGR). Stationary phase data can begin to show a decline and make it difficult to discern which data to include in the analysis of the growth curve, a factor that influences the calculated values of the growth parameters. In contradistinction, the quasi-chemical kinetics model provides additional capabilities in microbial modelling and fits growth-death kinetics (all four phases of the microbial lifecycle continuously) for a general set of microorganisms in a variety of actual food substrates. The quasi-chemical model is differential equations (ODEs) that derives from a hypothetical four-step chemical mechanism involving an antagonistic metabolite (quorum sensing) and successfully fits the kinetics of pathogens (Staphylococcus aureus, Escherichia coli and Listeria monocytogenes) in various foods (bread, turkey meat, ham and cheese) as functions of different hurdles (a(w), pH, temperature and anti-microbial lactate). The calculated value of the MGR depends on whether growth-death data or only growth data are used in the fitting procedure. The quasi-chemical kinetics model is also exploited for use with the novel food processing technology of high-pressure processing. The high-pressure inactivation kinetics of E. coli are explored in a model food system over the pressure (P) range of 207-345 MPa (30,000-50,000 psi) and the temperature (T) range of 30-50 degrees C. In relatively low combinations of P and T, the inactivation curves are non-linear and exhibit a shoulder prior to a more rapid rate of microbial destruction. In the higher P, T regime, the inactivation plots tend to be linear. In all cases, the quasi-chemical model successfully fit the linear and curvi-linear inactivation plots for E. coli in model food systems. The experimental data and the quasi-chemical mathematical model described herein are candidates for inclusion in ComBase, the developing database that combines data and models from the USDA Pathogen Modeling Program and the UK Food MicroModel.

Application of a validated stability-indicating densitometric thin-layer chromatographic method to stress degradation studies on moxifloxacin.

PubMed

Motwani, Sanjay K; Khar, Roop K; Ahmad, Farhan J; Chopra, Shruti; Kohli, K; Talegaonkar, S

2007-01-16

A simple, sensitive, selective, precise and stability-indicating high-performance thin-layer chromatographic (HPTLC) method for densitometric determination of moxifloxacin both as a bulk drug and from pharmaceutical formulation was developed and validated as per the International Conference on Harmonization (ICH) guidelines. The method employed TLC aluminium plates pre-coated with silica gel 60F-254 as the stationary phase and the mobile phase consisted of n-propanol-ethanol-6M ammonia solution (4:1:2, v/v/v). Densitometric analysis of moxifloxacin was carried out in the absorbance mode at 298 nm. Compact spots for moxifloxacin were found at R(f) value of 0.58+/-0.02. The linear regression analysis data for the calibration plots showed good linear relationship with r=0.9925 in the working concentration range of 100-800 ng spot(-1). The method was validated for precision, accuracy, ruggedness, robustness, specificity, recovery, limit of detection (LOD) and limit of quantitation (LOQ). The LOD and LOQ were 3.90 and 11.83 ng spot(-1), respectively. Drug was subjected to acid and alkali hydrolysis, oxidation, dry heat, wet heat treatment and photodegradation. All the peaks of degradation products were well resolved from the standard drug with significantly different R(f) values. Statistical analysis proves that the developed HPTLC method is reproducible and selective. As the method could effectively separate the drug from its degradation products, it can be employed as stability-indicating one. Moreover, the proposed HPTLC method was utilized to investigate the kinetics of the acidic and alkaline degradation processes at different temperatures. Arrhenius plot was constructed and apparent pseudo-first-order rate constant, half-life and activation energy were calculated. In addition the pH-rate profile for degradation of moxifloxacin in constant ionic strength buffer solutions within the pH range 1.2-10.8 was studied.

Kinetics of Hole Nucleation in Biomembrane Rupture

PubMed Central

Evans, Evan; Smith, Benjamin A

2011-01-01

The core component of a biological membrane is a fluid-lipid bilayer held together by interfacial-hydrophobic and van der Waals interactions, which are balanced for the most part by acyl chain entropy confinement. If biomembranes are subjected to persistent tensions, an unstable (nanoscale) hole will emerge at some time to cause rupture. Because of the large energy required to create a hole, thermal activation appears to be requisite for initiating a hole and the activation energy is expected to depend significantly on mechanical tension. Although models exist for the kinetic process of hole nucleation in tense membranes, studies of membrane survival have failed to cover the ranges of tension and lifetime needed to critically examine nucleation theory. Hence, rupturing giant (~20 μm) membrane vesicles ultra-slowly to ultra-quickly with slow to fast ramps of tension, we demonstrate a method to directly quantify kinetic rates at which unstable holes form in fluid membranes, at the same time providing a range of kinetic rates from < 0.01 s−1 to > 100 s−1. Measuring lifetimes of many hundreds of vesicles, each tensed by precision control of micropipet suction, we have determined the rates of failure for vesicles made from several synthetic phospholipids plus 1:1 mixtures of phospho- and sphingo-lipids with cholesterol, all of which represent prominent constituents of eukaryotic cell membranes. Plotted on a logarithmic scale, the failure rates for vesicles are found to rise dramatically with increase of tension. Converting the experimental profiles of kinetic rates into changes of activation energy versus tension, we show that the results closely match expressions for thermal activation derived from a combination of meso-scale theory and molecular-scale simulations of hole formation. Moreover, we demonstrate a generic approach to transform analytical fits of activation energies obtained from rupture experiments into energy landscapes characterizing the process hole nucleation along the reaction coordinate defined by hole size. PMID:21966242

Kinetics of organic transformations under mild aqueous conditions: implications for the origin of life and its metabolism

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

2004-01-01

The rates of thermal transformation of organic molecules containing carbon, hydrogen, and oxygen were systematically examined in order to identify the kinetic constraints that governed origin-of-life organic chemistry under mild aqueous conditions. Arrhenius plots of the kinetic data were used to estimate the reaction of half-lifes at 50 degrees C. This survey showed that hydrocarbons and organic substances containing a single oxygenated group were kinetically the most stable; whereas organic substances containing two oxygenated groups in which one group was an alpha- or beta-positioned carbonyl group were the most reactive. Compounds with an alpha- or beta-positioned carbonyl group (aldehyde or ketone) had rates of reaction that were up to 10(24)-times faster than rates of similar molecules lacking the carbonyl group. This survey of organic reactivity, together with estimates of the molecular containment properties of lipid vesicles and liquid spherules, indicates that an origins process in a small domain that used C,H,O-intermediates had to be catalytic and use the most reactive organic molecules to prevent escape of its reaction intermediates.

Factors affecting hydrogen-tunneling contribution in hydroxylation reactions promoted by oxoiron(IV) porphyrin π-cation radical complexes.

PubMed

Cong, Zhiqi; Kinemuchi, Haruki; Kurahashi, Takuya; Fujii, Hiroshi

2014-10-06

Hydrogen atom transfer with a tunneling effect (H-tunneling) has been proposed to be involved in aliphatic hydroxylation reactions catalyzed by cytochrome P450 and synthetic heme complexes as a result of the observation of large hydrogen/deuterium kinetic isotope effects (KIEs). In the present work, we investigate the factors controlling the H-tunneling contribution to the H-transfer process in hydroxylation reaction by examining the kinetics of hydroxylation reactions at the benzylic positions of xanthene and 1,2,3,4-tetrahydronaphthalene by oxoiron(IV) 5,10,15,20-tetramesitylporphyrin π-cation radical complexes ((TMP(+•))Fe(IV)O(L)) under single-turnover conditions. The Arrhenius plots for these hydroxylation reactions of H-isotopomers have upwardly concave profiles. The Arrhenius plots of D-isotopomers, clear isosbestic points, and product analysis rule out the participation of thermally dependent other reaction processes in the concave profiles. These results provide evidence for the involvement of H-tunneling in the rate-limiting H-transfer process. These profiles are simulated using an equation derived from Bell's tunneling model. The temperature dependence of the KIE values (k(H)/k(D)) determined for these reactions indicates that the KIE value increases as the reaction temperature becomes lower, the bond dissociation energy (BDE) of the C-H bond of a substrate becomes higher, and the reactivity of (TMP(+•))Fe(IV)O(L) decreases. In addition, we found correlation of the slope of the ln(k(H)/k(D)) - 1/T plot and the bond strengths of the Fe═O bond of (TMP(+•))Fe(IV)O(L) estimated from resonance Raman spectroscopy. These observations indicate that these factors modulate the extent of the H-tunneling contribution by modulating the ratio of the height and thickness of the reaction barrier.

Novel Starch-PVA Polymer for Microparticle Preparation and Optimization Using Factorial Design Study

PubMed Central

Chattopadhyay, Helen; De, Amit Kumar; Datta, Sriparna

2015-01-01

The aim of our present work was to optimize the ratio of a very novel polymer, starch-polyvinyl alcohol (PVA), for controlled delivery of Ornidazole. Polymer-coated drug microparticles were prepared by emulsion method. Microscopic study, scanning electron microscopic study, and atomic force microscopic study revealed that the microparticles were within 10 micrometers of size with smooth spherical shape. The Fourier transform infrared spectroscopy showed absence of drug polymer interaction. A statistical 32 full factorial design was used to study the effect of different concentration of starch and PVA on the drug release profile. The three-dimensional plots gave us an idea about the contribution of each factor on the release kinetics. Hence this novel polymer of starch and polyvinyl alcohol can be utilized for control release of the drug from a targeted delivery device. PMID:27347511

Regulation of Glucose Transport in Quiescent, Lactating, and Neoplastic Mammary Epithelia

DTIC Science & Technology

1998-10-01

17000g pellet iodixanol density gradient was collected and solubilized with 1.25% dodecyl maltoside in the presence of 6- aminocaproic acid . After a...regulatory properties, tissue distributions, and kinetics. However, they are all integral membrane proteins containing approximately 500 amino acids ...Hydropathy plots based on amino acid sequences predicted from cDNA sequence suggest that all share a common topology, which includes cytoplasmic N- and C

Disentangling random thermal motion of particles and collective expansion of source from transverse momentum spectra in high energy collisions

NASA Astrophysics Data System (ADS)

Wei, Hua-Rong; Liu, Fu-Hu; Lacey, Roy A.

2016-12-01

In the framework of a multisource thermal model, we describe experimental results of the transverse momentum spectra of final-state light flavor particles produced in gold-gold (Au-Au), copper-copper (Cu-Cu), lead-lead (Pb-Pb), proton-lead (p-Pb), and proton-proton (p -p) collisions at various energies, measured by the PHENIX, STAR, ALICE, and CMS Collaborations, by using the Tsallis-standard (Tsallis form of Fermi-Dirac or Bose-Einstein), Tsallis, and two- or three-component standard distributions which can be in fact regarded as different types of ‘thermometers’ or ‘thermometric scales’ and ‘speedometers’. A central parameter in the three distributions is the effective temperature which contains information on the kinetic freeze-out temperature of the emitting source and reflects the effects of random thermal motion of particles as well as collective expansion of the source. To disentangle both effects, we extract the kinetic freeze-out temperature from the intercept of the effective temperature (T) curve as a function of particle’s rest mass (m 0) when plotting T versus m 0, and the mean transverse flow velocity from the slope of the mean transverse momentum (< {p}T> ) curve as a function of mean moving mass (\\overline{m}) when plotting < {p}T> versus \\overline{m}.

Characterization of peak capacity of microbore liquid chromatography columns using gradient kinetic plots.

PubMed

Hetzel, Terence; Blaesing, Christina; Jaeger, Martin; Teutenberg, Thorsten; Schmidt, Torsten C

2017-02-17

The performance of micro-liquid chromatography columns with an inner diameter of 0.3mm was investigated on a dedicated micro-LC system for gradient elution. Core-shell as well as fully porous particle packed columns were compared on the basis of peak capacity and gradient kinetic plot limits. The results for peak capacity showed the superior performance of columns packed with sub-2μm fully porous particles compared to 3.0μm fully porous and 2.7μm core-shell particles within a range of different gradient time to column void time ratios. For ultra-fast chromatography a maximum peak capacity of 16 can be obtained using a 30s gradient for the sub-2μm fully porous particle packed column. A maximum peak capacity of 121 can be achieved using a 5min gradient. In addition, the influence of an alternative detector cell on the basis of optical waveguide technology and contributing less to system variance was investigated showing an increased peak capacity for all applied gradient time/column void time ratios. Finally, the influence of pressure was evaluated indicating increased peak capacity for maximum performance whereas a limited benefit for ultra-fast chromatography with gradient times below 30s was observed. Copyright © 2017 Elsevier B.V. All rights reserved.

UAV remote sening for precision agriculture

NASA Astrophysics Data System (ADS)

Vigneau, Nathalie; Chéron, Corentin; Mainfroy, Florent; Faroux, Romain

2014-05-01

Airinov offers to farmers, scientists and experimenters (plant breeders, etc.) its technical skills about UAVs, cartography and agronomic remote sensing. The UAV is a 2-m-wingspan flying wing. It can carry away either a RGB camera or a multispectral sensor, which records reflectance in 4 spectral bands. The spectral characteristics of the sensor are modular. Each spectral band is comprised between 400 and 850 nm and the FWHM (Full Width at Half Maximum) is between 10 and 40 nm. The spatial resolution varies according to sensor, flying height and user needs from 15cm/px for multispectral sensor at 150m to 1.5cm/px for RGB camera at 50m. The flight is totally automatic thanks to on-board autopilot, IMU (Inertial Measurement Unit) and GPS. Data processing (unvignetting, mosaicking, correction in reflectance) leads to agronomic variables as LAI (Leaf Area Index) or chlorophyll content for barley, wheat, rape and maize as well as vegetation indices as NDVI (Normalized Difference Vegetation Index). Using these data, Airinov can product advices for farmers as nitrogen preconisation for rape. For scientists, Airinov offers trial plot monitoring by micro-plots vectorisation and numerical data exctraction micro-plot by micro-plot. This can lead to kinetic curve for LAI or NDVI to compare cover establishment for different genotypes for example. Airinov's system is a new way to monitor plots with a lot of data (biophysical or biochemical parameters) at high rate, high spatial resolution and high precision.

Identifying hidden common causes from bivariate time series: a method using recurrence plots.

PubMed

Hirata, Yoshito; Aihara, Kazuyuki

2010-01-01

We propose a method for inferring the existence of hidden common causes from observations of bivariate time series. We detect related time series by excessive simultaneous recurrences in the corresponding recurrence plots. We also use a noncoverage property of a recurrence plot by the other to deny the existence of a directional coupling. We apply the proposed method to real wind data.

Double sampling to estimate density and population trends in birds

USGS Publications Warehouse

Bart, Jonathan; Earnst, Susan L.

2002-01-01

We present a method for estimating density of nesting birds based on double sampling. The approach involves surveying a large sample of plots using a rapid method such as uncorrected point counts, variable circular plot counts, or the recently suggested double-observer method. A subsample of those plots is also surveyed using intensive methods to determine actual density. The ratio of the mean count on those plots (using the rapid method) to the mean actual density (as determined by the intensive searches) is used to adjust results from the rapid method. The approach works well when results from the rapid method are highly correlated with actual density. We illustrate the method with three years of shorebird surveys from the tundra in northern Alaska. In the rapid method, surveyors covered ~10 ha h-1 and surveyed each plot a single time. The intensive surveys involved three thorough searches, required ~3 h ha-1, and took 20% of the study effort. Surveyors using the rapid method detected an average of 79% of birds present. That detection ratio was used to convert the index obtained in the rapid method into an essentially unbiased estimate of density. Trends estimated from several years of data would also be essentially unbiased. Other advantages of double sampling are that (1) the rapid method can be changed as new methods become available, (2) domains can be compared even if detection rates differ, (3) total population size can be estimated, and (4) valuable ancillary information (e.g. nest success) can be obtained on intensive plots with little additional effort. We suggest that double sampling be used to test the assumption that rapid methods, such as variable circular plot and double-observer methods, yield density estimates that are essentially unbiased. The feasibility of implementing double sampling in a range of habitats needs to be evaluated.

Microarray-based Resequencing of Multiple Bacillus anthracis Isolates

DTIC Science & Technology

2004-12-17

generated an Unweighted Pair Group Method Arithmetic Mean ( UPGMA ) tree (see methods [56]; Figure 3). The strains group together in a manner broadly similar...was created using DNADIST, plotted as a UPGMA tree using NEIGHBOR and the tree plotted using DRAWGRAM [56]. The B1 strain A0465 was used as an...distance matrix was created using DNADIST, plotted as a UPGMA tree using NEIGHBOR and the tree plotted using DRAWGRAM [57]. Additional data files The

Exploring and accounting for publication bias in mental health: a brief overview of methods.

PubMed

Mavridis, Dimitris; Salanti, Georgia

2014-02-01

OBJECTIVE Publication bias undermines the integrity of published research. The aim of this paper is to present a synopsis of methods for exploring and accounting for publication bias. METHODS We discussed the main features of the following methods to assess publication bias: funnel plot analysis; trim-and-fill methods; regression techniques and selection models. We applied these methods to a well-known example of antidepressants trials that compared trials submitted to the Food and Drug Administration (FDA) for regulatory approval. RESULTS The funnel plot-related methods (visual inspection, trim-and-fill, regression models) revealed an association between effect size and SE. Contours of statistical significance showed that asymmetry in the funnel plot is probably due to publication bias. Selection model found a significant correlation between effect size and propensity for publication. CONCLUSIONS Researchers should always consider the possible impact of publication bias. Funnel plot-related methods should be seen as a means of examining for small-study effects and not be directly equated with publication bias. Possible causes for funnel plot asymmetry should be explored. Contours of statistical significance may help disentangle whether asymmetry in a funnel plot is caused by publication bias or not. Selection models, although underused, could be useful resource when publication bias and heterogeneity are suspected because they address directly the problem of publication bias and not that of small-study effects.

Comparison of the efficacy of steam sterilization indicators.

PubMed Central

Lee, C H; Montville, T J; Sinskey, A J

1979-01-01

Twenty-one commercially available chemical steam sterilization indicators were processed in an empty autoclave for various times at temperatures between 240 and 270 degrees F (ca. 116 and 132 degrees C). The time required to reach a sterilized reading at each temperature was plotted on a semilogarithmic time-temperature plot and compared with the time-temperature sterilization curve for Bacillus stearothermophilus. Five of the indicators had time-temperature kinetics similar to those of B. stearothermophilus, but three of these overestimated the effect of processing. Two of the indicators overestimated the effect of processing and were less sensitive to temperature changes when was B. stearothermophilus. Thirteen of the indicators had time-temperature curves that crossed the B. stearothermophilus plot. One indicator produced such ambiguous results that no determinations could be made with it. Out of 21 indicators tested, only 2 appear to be capable of accurately integrating the time-temperature effect at temperatures between 240 and 270 degrees F. The other indicators should be used only after careful analysis of their suitability for use at a given temperature. PMID:485144

Small scale rainfall simulators: Challenges for a future use in soil erosion research

NASA Astrophysics Data System (ADS)

Ries, Johannes B.; Iserloh, Thomas; Seeger, Manuel

2013-04-01

Rainfall simulation on micro-plot scale is a method used worldwide to assess the generation of overland flow, soil erosion, infiltration and interrelated processes such as soil sealing, crusting, splash and redistribution of solids and solutes. The produced data are of great significance not only for the analysis of the simulated processes, but also as a source of input-data for soil erosion modelling. The reliability of the data is therefore of paramount importance, and quality management of rainfall simulation procedure a general responsibility of the rainfall simulation community. This was an accepted outcome at the "International Rainfall Simulator Workshop 2011" at Trier University. The challenges of the present and near future use of small scale rainfall simulations concern the comparability of results and scales, the quality of the data for soil erosion modelling, and further technical developments to overcome physical limitations and constraints. Regarding the high number of research questions, different fields of application, and due to the great technical creativity of researchers, a large number of different types of rainfall simulators is available. But each of the devices produces a different rainfall, leading to different kinetic energy values influencing soil surface and erosion processes. Plot sizes are also variable, as well as the experimental simulation procedures. As a consequence, differing runoff and erosion results are produced. The presentation summarises the three important aspects of rainfall simulations, following a processual order: 1. Input-factor "rain" and its calibration 2. Surface-factor "plot" and its documentation 3. Output-factors "runoff" and "sediment concentration" Finally, general considerations about the limitations and challenges for further developments and applications of rainfall simulation data are presented.

Qualitative comparison of soil erosion, runoff and infiltration coefficients using small portable rainfall simulators in Germany, Spain and France

NASA Astrophysics Data System (ADS)

Rodrigo Comino, Jesús; Iserloh, Thomas; Morvan, Xavier; Malam Issa, Oumarou; Naisse, Christophe; Keesstra, Saskia; Cerdà, Artemi; Prosdocimi, Massimo; Arnáez, José; Lasanta, Teodoro; Concepción Ramos, María; José Marqués, María; Ruiz Colmenero, Marta; Bienes, Ramón; Damián Ruiz Sinoga, José; Seeger, Manuel; Ries, Johannes B.

2016-04-01

Small portable rainfall simulators are considered as a useful tool to analyze soil erosion processes in cultivated lands. European research groups of Spain (Valencia, Málaga, Lleida, Madrid and La Rioja), France (Reims) or Germany (Trier) have used different rainfall simulators (varying in drop size distribution and fall velocities, kinetic energy, plot forms and sizes, and field of application)to study soil loss, surface flow, runoff and infiltration coefficients in different experimental plots (Valencia, Montes de Málaga, Penedès, Campo Real and La Rioja in Spain, Champagne in France and Mosel-Ruwer valley in Germany). The measurements and experiments developed by these research teams give an overview of the variety in the methodologies with rainfall simulations in studying the problem of soil erosion and describing the erosion features in different climatic environments, management practices and soil types. The aim of this study is: i) to investigate where, how and why researchers from different wine-growing regions applied rainfall simulations with successful results as a tool to measure soil erosion processes; ii) to make a qualitative comparison about the general soil erosion processes in European terroirs; iii) to demonstrate the importance of the development a standard method for soil erosion processes in vineyards, using rainfall simulators; iv) and to analyze the key factors that should be taken into account to carry out rainfall simulations. The rainfall simulations in all cases allowed knowing the infiltration capacity and the susceptibility of the soil to be detached and to generate sediment loads to runoff. Despite using small plots, the experiments were useful to analyze the influence of soil cover to reduce soil erosion and to make comparison between different locations or the influence of different soil characteristics.

Using T-Z plots as a graphical method to infer lithological variations from growth strata

NASA Astrophysics Data System (ADS)

Castelltort, Sébastien; Pochat, Stéphane; Van Den Driessche, Jean

2004-08-01

The 'T-Z plot' method consists of plotting the throw of sedimentary horizons across a growth fault versus their depth in the hanging wall. This method has been initially developed for the analysis of growth fault kinematics from seismic data. A brief analytical examination of such plots shows that they can also provide valuable information about the evolution of fault topography. When growth is a continuous process, stages of topography creation (fault scarp) and filling (of the space available in the hanging-wall) are related to non-dynamic (draping, mud-prone pelagic settling) and dynamic (sand-prone, dynamically deposited) sedimentation, respectively. In this case, the T-Z plot analysis becomes a powerful tool to predict major lithological variations on seismic profiles in faulted settings.

Design, synthesis, kinetic mechanism and molecular docking studies of novel 1-pentanoyl-3-arylthioureas as inhibitors of mushroom tyrosinase and free radical scavengers.

PubMed

Larik, Fayaz Ali; Saeed, Aamer; Channar, Pervaiz Ali; Muqadar, Urooj; Abbas, Qamar; Hassan, Mubashir; Seo, Sung-Yum; Bolte, Michael

2017-12-01

A series of novel 1-pentanoyl-3-arylthioureas was designed as new mushroom tyrosinase inhibitors and free radical scavengers. The title compounds were obtained in excellent yield and characterized by FTIR, 1 H NMR, 13 C NMR and X-ray crystallography in case of compound (4a). The inhibitory effects on mushroom tyrosinase and DPPH were evaluated and it was observed that 1-Pentanoyl-3-(4-methoxyphenyl) thiourea (4f) showed tyrosinase inhibitory activity (IC 50 1.568 ± 0.01 mM) comparable to Kojic acid (IC 50 16.051 ± 1.27 mM). Interestingly compound 4f exhibited higher antioxidant potential compared to other derivatives. The docking studies of synthesized 1-Pentanoyl-3-arylthioureas analogues were also carried out against tyrosinase protein (PDBID 2ZMX) to compare the binding affinities with IC 50 values. The predicted binding affinities are in good agreement with the IC 50 values as compound (4f) showed highest binding affinity (-7.50 kcal/mol) compared to others derivatives. The kinetic mechanism analyzed by Line-weavere Burk plots exhibited that compound (4f) inhibit the enzyme inhibits the tyrosinase non-competitively to form an enzyme inhibitor complex. The inhibition constants Ki calculated from Dixon plots for compound (4f) is 1.10 μM. It was also found from kinetic analysis that derivative 4f irreversible enzyme inhibitor complex. It is proposed on the basis of our investigation that title compound (4f) may serve as lead structure for the design of more potent tyrosinase inhibitors. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Rainfall and sheet power model for interrill erosion in steep slope

NASA Astrophysics Data System (ADS)

Shin, Seung Sook; Deog Park, Sand; Nam, Myeong Jun

2015-04-01

The two-phase process of interrill erosion consist of the splash and detachment of individual particles from soil mass by impact of raindrops and the transport by erosive running water. Most experimental results showed that the effect of interaction between rainfall impact and surface runoff increases soil erosion in low or gentle slope. Especially, the combination of rain splash and sheet flow is the dominant runoff and erosion mechanism occurring on most steep hillslopes. In this study, a rainfall simulation was conducted to evaluate interrill erosion in steep slope with cover or non-cover. The kinetic energy of raindrops of rainfall simulator was measured by disdrometer used to measure the drop size distribution and velocity of falling raindrops and showed about 0.563 rate of that calculated from empirical equation between rainfall kinetic energy and rainfall intensity. Surface and subsurface runoff and sediment yield depended on rainfall intensity, gradient of slope, and existence of cover. Sediment from steep plots under rainfall simulator is greatly reduced by existence of the strip cover that the kinetic energy of raindrop approximates to zero. Soil erosion in steep slope with non-cover was nearly 4.93 times of that measured in plots with strip cover although runoff was only 1.82 times. The equation of a rainfall and sheet power was used to evaluate sediment yields in steep slope with cover or non-cover. The power model successfully explained physical processes for interrill erosion that combination of raindrop impact and sheet flow increases greatly soil erosion in steep slope. This research was supported by Basic Science Research Program through the National Research Foundation of Korea(NRF) funded by the Ministry of Education, Science and Technology(No. 2013R1A1A3011962).

Mechanisms and distribution of ion channels in retinal ganglion cells: using temperature as an independent variable.

PubMed

Fohlmeister, Jürgen F; Cohen, Ethan D; Newman, Eric A

2010-03-01

Trains of action potentials of rat and cat retinal ganglion cells (RGCs) were recorded intracellularly across a temperature range of 7-37 degrees C. Phase plots of the experimental impulse trains were precision fit using multicompartment simulations of anatomically reconstructed rat and cat RGCs. Action potential excitation was simulated with a "Five-channel model" [Na, K(delayed rectifier), Ca, K(A), and K(Ca-activated) channels] and the nonspace-clamped condition of the whole cell recording was exploited to determine the channels' distribution on the dendrites, soma, and proximal axon. At each temperature, optimal phase-plot fits for RGCs occurred with the same unique channel distribution. The "waveform" of the electrotonic current was found to be temperature dependent, which reflected the shape changes in the experimental action potentials and confirmed the channel distributions. The distributions are cell-type specific and adequate for soma and dendritic excitation with a safety margin. The highest Na-channel density was found on an axonal segment some 50-130 microm distal to the soma, as determined from the temperature-dependent "initial segment-somadendritic (IS-SD) break." The voltage dependence of the gating rate constants remains invariant between 7 and 23 degrees C and between 30 and 37 degrees C, but undergoes a transition between 23 and 30 degrees C. Both gating-kinetic and ion-permeability Q10s remain virtually constant between 23 and 37 degrees C (kinetic Q10s = 1.9-1.95; permeability Q10s = 1.49-1.64). The Q10s systematically increase for T <23 degrees C (kinetic Q10 = 8 at T = 8 degrees C). The Na channels were consistently "sleepy" (non-Arrhenius) for T <8 degrees C, with a loss of spiking for T <7 degrees C.

Coarse-graining time series data: Recurrence plot of recurrence plots and its application for music

NASA Astrophysics Data System (ADS)

Fukino, Miwa; Hirata, Yoshito; Aihara, Kazuyuki

2016-02-01

We propose a nonlinear time series method for characterizing two layers of regularity simultaneously. The key of the method is using the recurrence plots hierarchically, which allows us to preserve the underlying regularities behind the original time series. We demonstrate the proposed method with musical data. The proposed method enables us to visualize both the local and the global musical regularities or two different features at the same time. Furthermore, the determinism scores imply that the proposed method may be useful for analyzing emotional response to the music.

Coarse-graining time series data: Recurrence plot of recurrence plots and its application for music.

PubMed

Fukino, Miwa; Hirata, Yoshito; Aihara, Kazuyuki

2016-02-01

We propose a nonlinear time series method for characterizing two layers of regularity simultaneously. The key of the method is using the recurrence plots hierarchically, which allows us to preserve the underlying regularities behind the original time series. We demonstrate the proposed method with musical data. The proposed method enables us to visualize both the local and the global musical regularities or two different features at the same time. Furthermore, the determinism scores imply that the proposed method may be useful for analyzing emotional response to the music.

Validity of the t-plot method to assess microporosity in hierarchical micro/mesoporous materials.

PubMed

Galarneau, Anne; Villemot, François; Rodriguez, Jeremy; Fajula, François; Coasne, Benoit

2014-11-11

The t-plot method is a well-known technique which allows determining the micro- and/or mesoporous volumes and the specific surface area of a sample by comparison with a reference adsorption isotherm of a nonporous material having the same surface chemistry. In this paper, the validity of the t-plot method is discussed in the case of hierarchical porous materials exhibiting both micro- and mesoporosities. Different hierarchical zeolites with MCM-41 type ordered mesoporosity are prepared using pseudomorphic transformation. For comparison, we also consider simple mechanical mixtures of microporous and mesoporous materials. We first show an intrinsic failure of the t-plot method; this method does not describe the fact that, for a given surface chemistry and pressure, the thickness of the film adsorbed in micropores or small mesopores (< 10σ, σ being the diameter of the adsorbate) increases with decreasing the pore size (curvature effect). We further show that such an effect, which arises from the fact that the surface area and, hence, the free energy of the curved gas/liquid interface decreases with increasing the film thickness, is captured using the simple thermodynamical model by Derjaguin. The effect of such a drawback on the ability of the t-plot method to estimate the micro- and mesoporous volumes of hierarchical samples is then discussed, and an abacus is given to correct the underestimated microporous volume by the t-plot method.

Kinetics of methane hydrate decomposition studied via in situ low temperature X-ray powder diffraction.

PubMed

Everett, S Michelle; Rawn, Claudia J; Keffer, David J; Mull, Derek L; Payzant, E Andrew; Phelps, Tommy J

2013-05-02

Gas hydrate is known to have a slowed decomposition rate at ambient pressure and temperatures below the melting point of ice. As hydrate exothermically decomposes, gas is released and water of the clathrate cages transforms into ice. Based on results from the decomposition of three nominally similar methane hydrate samples, the kinetics of two regions, 180-200 and 230-260 K, within the overall decomposition range 140-260 K, were studied by in situ low temperature X-ray powder diffraction. The kinetic rate constants, k(a), and the reaction mechanisms, n, for ice formation from methane hydrate were determined by the Avrami model within each region, and activation energies, E(a), were determined by the Arrhenius plot. E(a) determined from the data for 180-200 K was 42 kJ/mol and for 230-260 K was 22 kJ/mol. The higher E(a) in the colder temperature range was attributed to a difference in the microstructure of ice between the two regions.

Evidence for tunneling in base-catalyzed isomerization of glyceraldehyde to dihydroxyacetone by hydride shift under formose conditions.

PubMed

Cheng, Liang; Doubleday, Charles; Breslow, Ronald

2015-04-07

Hydrogen atom transfer reactions between the aldose and ketose are key mechanistic features in formose chemistry by which formaldehyde is converted to higher sugars under credible prebiotic conditions. For one of these transformations, we have investigated whether hydrogen tunneling makes a significant contribution to the mechanism by examining the deuterium kinetic isotope effect associated with the hydrogen transfer during the isomerization of glyceraldehyde to the corresponding dihydroxyacetone. To do this, we developed a quantitative HPLC assay that allowed us to measure the apparent large intrinsic kinetic isotope effect. From the Arrhenius plot of the kinetic isotope effect, the ratio of the preexponential factors AH/AD was 0.28 and the difference in activation energies Ea(D) - Ea(H) was 9.1 kJ·mol(-1). All these results imply a significant quantum-mechanical tunneling component in the isomerization mechanism. This is supported by multidimensional tunneling calculations using POLYRATE with small curvature tunneling.

A PICKSC Science Gateway for enabling the common plasma physicist to run kinetic software

NASA Astrophysics Data System (ADS)

Hu, Q.; Winjum, B. J.; Zonca, A.; Youn, C.; Tsung, F. S.; Mori, W. B.

2017-10-01

Computer simulations offer tremendous opportunities for studying plasmas, ranging from simulations for students that illuminate fundamental educational concepts to research-level simulations that advance scientific knowledge. Nevertheless, there is a significant hurdle to using simulation tools. Users must navigate codes and software libraries, determine how to wrangle output into meaningful plots, and oftentimes confront a significant cyberinfrastructure with powerful computational resources. Science gateways offer a Web-based environment to run simulations without needing to learn or manage the underlying software and computing cyberinfrastructure. We discuss our progress on creating a Science Gateway for the Particle-in-Cell and Kinetic Simulation Software Center that enables users to easily run and analyze kinetic simulations with our software. We envision that this technology could benefit a wide range of plasma physicists, both in the use of our simulation tools as well as in its adaptation for running other plasma simulation software. Supported by NSF under Grant ACI-1339893 and by the UCLA Institute for Digital Research and Education.

Analysis of atmospheric flow over a surface protrusion using the turbulence kinetic energy equation with reference to aeronautical operating systems

NASA Technical Reports Server (NTRS)

Frost, W.; Harper, W. L.

1975-01-01

Flow over surface obstructions can produce significantly large wind shears such that adverse flying conditions can occur for aeronautical systems (helicopters, STOL vehicles, etc.). Atmospheric flow fields resulting from a semi-elliptical surface obstruction in an otherwise horizontally homogeneous statistically stationary flow are modelled with the boundary-layer/Boussinesq-approximation of the governing equation of fluid mechanics. The turbulence kinetic energy equation is used to determine the dissipative effects of turbulent shear on the mean flow. Iso-lines of turbulence kinetic energy and turbulence intensity are plotted in the plane of the flow and highlight regions of high turbulence intensity in the stagnation zone and sharp gradients in intensity along the transition from adverse to favourable pressure gradient. Discussion of the effects of the disturbed wind field in CTOL and STOL aircraft flight path and obstruction clearance standards is given. The results indicate that closer inspection of these presently recommended standards as influenced by wind over irregular terrains is required.

Dynamics of C2H 2 3 +→H++H++C 2 + investigated by 50-keV/u Ne8 + impact

NASA Astrophysics Data System (ADS)

Xu, S.; Zhu, X. L.; Feng, W. T.; Guo, D. L.; Zhao, Q.; Yan, S.; Zhang, P.; Zhao, D. M.; Gao, Y.; Zhang, S. F.; Yang, J.; Ma, X.

2018-06-01

Breakup dynamics of C2H 2 3 + → H++H++C 2 + induced by 50-keV/u Ne8 + ion impact is investigated employing a reaction microscope. All three ionic fragments in the final state are detected in coincidence, and their momentum vectors as well as the kinetic energies are determined. The kinetic-energy correlation spectrum of the two protons displays very rich structures. Utilizing the Newton diagrams and the Dalitz plots, different dissociation mechanisms corresponding to these structures are identified. It was found that, besides the concerted and sequential breakup, fragmentation mechanisms associated with different vibration modes including molecular bending and asymmetric stretching also make significant contributions. We analyzed the correlation between different fragmentation mechanisms and the kinetic-energy release (KER) and found that the sequential process occurs with higher KER while, in contrast, the concerted process mainly contributes to the lower KER. This behavior is entirely opposite to the breakup of the CO2 molecule.

Kinetics of Methane Hydrate Decomposition Studied via in Situ Low Temperature X-ray Powder Diffraction

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

Everett, Susan M; Rawn, Claudia J; Keffer, David J.

Gas hydrates are known to have a slowed decomposition rate at ambient pressure and temperatures below the melting point of ice termed self-preservation or anomalous preservation. As hydrate exothermically decomposes, gas is released and water of the clathrate cages transforms into ice. Two regions of slowed decomposition for methane hydrate, 180 200 K and 230 260 K, were observed, and the kinetics were studied by in situ low temperature x-ray powder diffraction. The kinetic constants for ice formation from methane hydrate were determined by the Avrami model within each region and activation energies, Ea, were determined by the Arrhenius plot.more » Ea determined from the data for 180 200 K was 42 kJ/mol and for 230 260 K was 22 kJ/mol. The higher Ea in the colder temperature range was attributed to a difference in the microstructure of ice between the two regions.« less

Oxygen Activation and Photoelectrochemical Oxidation on Oxide Surfaces

DTIC Science & Technology

2013-12-04

electrolysis followed by product determination from mass spectroscopy showed that acetophenone was produced with a 95% Faradaic efficiency. The H/D kinetic...vs. NHE) 10 electrode: scan rate, 100mV/s. (b) Plot of catalytic currents during electrolysis at −1.38 V, icat (background subtracted), vs...controlled potential electrolysis at 3.0 V at two boron doped diamond electrodes (~0.85 cm2). Red line: background current without added catalyst

Thermal degradation of Lewis acid complexed LDPE films

NASA Astrophysics Data System (ADS)

Sreelatha, K.; Predeep, P.

2017-06-01

The study highlights the thermal behavior of the semiconducting LDPE films synthesized by SbCl5 doping. The structural peculiarities and the responses of the structure to energetic modifications are studied. TGA and DTG curves are used to determine the thermal stability of the material. Degradation kinetics is elucidated. Activation energy and the entropy of activation for the degradation of the samples are calculated using Coats-Redfern plots and the samples show appreciable thermal stability.

Establishment of monitoring plots and evaluation of trees injured by ozone

Treesearch

Daniel Duriscoe; Kenneth Stolte; John Pronos

1996-01-01

By establishing long–term monitoring plots, it is possible to record environmental and biological conditions of the plot and individual trees, evaluate the condition of crowns of trees in the plot, and determine the extent of ozone injury to western conifers. This chapter recommends various methods for recording data and selecting plots, and provides information for...

Boundary pint corrections for variable radius plots - simulation results

Treesearch

Margaret Penner; Sam Otukol

2000-01-01

The boundary plot problem is encountered when a forest inventory plot includes two or more forest conditions. Depending on the correction method used, the resulting estimates can be biased. The various correction alternatives are reviewed. No correction, area correction, half sweep, and toss-back methods are evaluated using simulation on an actual data set. Based on...

Nucleation of polystyrene latex particles in the presence of gamma-methacryloxypropyltrimethoxysilane: functionalized silica particles.

PubMed

Bourgeat-Lami, Elodie; Insulaire, Mickaelle; Reculusa, Stéphane; Perro, Adeline; Ravaine, Serge; Duguet, Etienne

2006-02-01

Silica/polystyrene nanocomposite particles with different morphologies were synthesized through emulsion polymerization of styrene in the presence of silica particles previously modified by gamma-methacryloxypropyltrimethoxysilane (MPS). Grafting of the silane molecule was performed by direct addition of MPS to the aqueous silica suspension in the presence of an anionic surfactant under basic conditions. The MPS grafting density on the silica surface was determined using the depletion method and plotted against the initial MPS concentration. The influence of the MPS grafting density, the silica particles size and concentration and the nature of the surfactant on the polymerization kinetics and the particles morphology was investigated. When the polymerization was performed in the presence of an anionic surfactant, transmission electron microscopy images showed the formation of polymer spheres around silica for MPS grafting densities lower than typically 1 micromole x m(-2) while the conversion versus time curves indicated a strong acceleration effect under such conditions. In contrast, polymerizations performed in the presence of a larger amount of MPS moieties or in the presence of a non ionic emulsifier resulted in the formation of "excentered" core-shell morphologies and lower polymerization rates. The paper identifies the parameters that allow to control particles morphology and polymerization kinetics and describes the mechanism of formation of the nanocomposite colloids.

Implications of drying temperature and humidity on the drying kinetics of seaweed

NASA Astrophysics Data System (ADS)

Ali, Majid Khan Majahar; Fudholi, Ahmad; Muthuvalu, M. S.; Sulaiman, Jumat; Yasir, Suhaimi Md

2017-11-01

A Low Temperature and Humidity Chamber Test tested in the Solar Energy Laboratory, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, Selangor, Malaysia. Experiments are attempted to study the effect of drying air temperature and humidity on the drying kinetics of seaweed Kappaphycus species Striatum besides to develop a model to estimate the drying curves. Simple method using a excel software is used in the analysis of raw data obtained from the drying experiment. The values of the parameters a, n and the constant k for the models are determined using a plot of curve drying models. Three different drying models are compared with experiment data seaweed drying at 30, 40, 50 and 60°C and relative humidity 20, 30 and 40% for seaweed. The higher drying temperatures and low relative humidity effects the moisture content that will be rapidly reduced. The most suitable model is selected to best describe the drying behavior of seaweed. The values of the coefficient of determination (R2), mean bias error (MBE) and root mean square error (RMSE) are used to determine the goodness or the quality of the fit. The Page model is showed a better fit to drying seaweed. The results from this study crucial for solar dryer development on pilot scale in Malaysia.

Very high pressure combustion; Reaction propagation rates of nitromethane within a diamond anvil cell

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

Rice, S.F.; Foltz, M.F.

1991-11-01

This paper reports on the combustion-front propagation rate of nitromethane that has been examined to pressures of 40 GPa. A new and general technique involving pulsed laser ignition of an energetic material within a diamond anvil cell and a method for monitoring the rapid decomposition of nitromethane and other explosives to more stable chemical products is described in detail. Nitromethane is shown to exhibit a flame propagation rate that increases smoothly to 100 m/s at 30 GPa as a function of pressure. Above 30 GPa, the final solid-state combustion products change dramatically and the flame propagation rate begins to decrease.more » The combustion-front propagation rate is analyzed in terms of an existing condensed-phase model that predicts a relationship between the front propagation rate, U, and the pressure derivative of the chemical kinetic activation energy, dE{sub a}/dP, such that a plot of logU{sup 2} vs. P should be linear. The activation energy is analyzed to yield an effective volume of activation, {Delta}V, of {minus}3.4 ml/mol. The chemical kinetic parameters determined from the combustion-front propagation rate analysis of solid high-pressure nitromethane is compared with results from other thermal decomposition studies of this prototypic molecular explosive.« less

Interaction of D2 with H2O amorphous ice studied by temperature-programmed desorption experiments.

PubMed

Amiaud, L; Fillion, J H; Baouche, S; Dulieu, F; Momeni, A; Lemaire, J L

2006-03-07

The gas-surface interaction of molecular hydrogen D2 with a thin film of porous amorphous solid water (ASW) grown at 10 K by slow vapor deposition has been studied by temperature-programmed-desorption (TPD) experiments. Molecular hydrogen diffuses rapidly into the porous network of the ice. The D2 desorption occurring between 10 and 30 K is considered here as a good probe of the effective surface of ASW interacting with the gas. The desorption kinetics have been systematically measured at various coverages. A careful analysis based on the Arrhenius plot method has provided the D2 binding energies as a function of the coverage. Asymmetric and broad distributions of binding energies were found, with a maximum population peaking at low energy. We propose a model for the desorption kinetics that assumes a complete thermal equilibrium of the molecules with the ice film. The sample is characterized by a distribution of adsorption sites that are filled according to a Fermi-Dirac statistic law. The TPD curves can be simulated and fitted to provide the parameters describing the distribution of the molecules as a function of their binding energy. This approach contributes to a correct description of the interaction of molecular hydrogen with the surface of possibly porous grain mantles in the interstellar medium.

Synthesis, characterization and non-isothermal decomposition kinetic of a new galactochloralose based polymer.

PubMed

Kök, Gökhan; Ay, Kadir; Ay, Emriye; Doğan, Fatih; Kaya, Ismet

2014-01-30

A glycopolymer, poly(3-O-methacroyl-5,6-O-isopropylidene-1,2-O-(S)-trichloroethylidene-α-d-galactofuranose) (PMIPTEG) was synthesized from the sugar-carrying methacrylate monomer, 3-O-methacroyl-5,6-O-isopropylidene-1,2-O-(S)-trichloroethylidene-α-d-galactofuranose (MIPTEG) via conventional free radical polymerization with AIBN in 1,4-dioxane. The structures of glycomonomer and their polymers were confirmed by UV-vis, FT-IR, (1)H NMR, (13)C NMR, GPC, TG/DTG-DTA, DSC, and SEM techniques. SEM images showed that PMIPTEG had a straight-chain length structure. On the other hand, the thermal decomposition kinetics of polymer were investigated by means of thermogravimetric analysis in dynamic nitrogen atmosphere at different heating rates. The apparent activation energies for thermal decomposition of the PMIPTEG were calculated using the Kissinger, Kim-Park, Tang, Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS) and Friedman methods and were found to be 100.15, 104.40, 102.0, 102.2, 103.2 and 99.6 kJ/mol, respectively. The most likely process mechanism related to the thermal decomposition stage of PMIPTEG was determined to be a Dn deceleration type in terms of master plots results. Copyright © 2013 Elsevier Ltd. All rights reserved.

Magnetic CuHCNPAN nano composite as an efficient adsorbent for strontium uptake

NASA Astrophysics Data System (ADS)

Mobtaker, Hossein Ghasemi; Pakzad, Seyed Mohammadreza; Yousefi, Taher

2018-06-01

An excellent composite was synthesized for sorption of strontium from solution. The composite (CuHCNPAN) components were copper hexacyanoferrate, magnetite and PAN. The XRD method confirmed the formation and presence of two crystalline phases of magnetite and copper hexacyanoferrate in composite. Particle sizes were determined by XRD and SEM methods. It was found that the particles were nano size. Some other methods such as FT IR, BET and TG methods were also used to determine the properties of the composite. The composite was used for sorption of strontium from solution. It was found that the kinetic of strontium sorption by the composite could be modeled by pseudo-second order. Among the isotherms applied to modeling the sorption in various concentrations, the Langmuir isotherm was founded to be more appropriate to fitting the experimental data. An excellent correlation coefficient was obtained (R2 > 0.98). The qmax for sorption of strontium ions which was calculated by Langmuir model was 80 mg/g. The thermodynamic parameters were calculated by determination of sorption in various temperatures and using the Vant Hoff plot. ΔG°, ΔH°, and ΔS° were calculated as -19.15, 2.28 and 0.071 kJ/mol respectively.

Reproducibility Between Brain Uptake Ratio Using Anatomic Standardization and Patlak-Plot Methods.

PubMed

Shibutani, Takayuki; Onoguchi, Masahisa; Noguchi, Atsushi; Yamada, Tomoki; Tsuchihashi, Hiroko; Nakajima, Tadashi; Kinuya, Seigo

2015-12-01

The Patlak-plot and conventional methods of determining brain uptake ratio (BUR) have some problems with reproducibility. We formulated a method of determining BUR using anatomic standardization (BUR-AS) in a statistical parametric mapping algorithm to improve reproducibility. The objective of this study was to demonstrate the inter- and intraoperator reproducibility of mean cerebral blood flow as determined using BUR-AS in comparison to the conventional-BUR (BUR-C) and Patlak-plot methods. The images of 30 patients who underwent brain perfusion SPECT were retrospectively used in this study. The images were reconstructed using ordered-subset expectation maximization and processed using an automatic quantitative analysis for cerebral blood flow of ECD tool. The mean SPECT count was calculated from axial basal ganglia slices of the normal side (slices 31-40) drawn using a 3-dimensional stereotactic region-of-interest template after anatomic standardization. The mean cerebral blood flow was calculated from the mean SPECT count. Reproducibility was evaluated using coefficient of variation and Bland-Altman plotting. For both inter- and intraoperator reproducibility, the BUR-AS method had the lowest coefficient of variation and smallest error range about the Bland-Altman plot. Mean CBF obtained using the BUR-AS method had the highest reproducibility. Compared with the Patlak-plot and BUR-C methods, the BUR-AS method provides greater inter- and intraoperator reproducibility of cerebral blood flow measurement. © 2015 by the Society of Nuclear Medicine and Molecular Imaging, Inc.

Raman and NMR kinetics study of the formation of amidoamines containing N-hydroxyethyl groups and investigations on their Cu(II) complexes in water

NASA Astrophysics Data System (ADS)

Bergamonti, Laura; Graiff, Claudia; Tegoni, Matteo; Predieri, Giovanni; Bellot-Gurlet, Ludovic; Lottici, Pier Paolo

2017-01-01

Three amidoamines containing the N-hydroxyethyl group (HOEt), namely (HOEt)2N(CH2)2C(O)NH2 (1), [(HOEt)2N(CH2)2C(O)NH]2CH2 (2) and HOEtN[(CH2)2C(O)NH2]2 (3) have been synthesized by reacting diethanolamine HOEt2NH with acrylamide and N,N‧-methylenebisacrylamide (respectively 1 and 2) and ethanolamine HOEtNH2 with acrylamide (3). Four other compounds corresponding to 1 and 2, but derived from sec-amines Me2NH (4 and 5) and Et2NH (6 and 7) have been prepared for the sake of comparison of the spectroscopic features. All compounds have been obtained by the well-known aza-Michael addition between an N-nucleophile and an activated vinyl group. The reaction in water between diethanolamine and acrylamide leading to 1 has been monitored in situ by Raman and NMR spectroscopy, both techniques confirming second order kinetics and giving values for kinetic constants in excellent agreement. The coordination ability of 1 and 2 towards Cu2 + in water has been studied by the Job's plot method. Spectroscopic data indicate that ligand 1 prevalently forms a 4:1 Ligand/Metal complex with a (N,O3) coordination set on the equatorial plane of Cu2 +, whereas ligand 2, containing two amide functionalities bridged by a methylene group, appears able to form a 1:1 Ligand/Metal chelate species, again with a (N,O3) donor set around copper.

Spatially Locating FIA Plots from Pixel Values

Treesearch

Greg C. Liknes; Geoffrey R. Holden; Mark D. Nelson; Ronald E. McRoberts

2005-01-01

The USDA Forest Service Forest Inventory and Analysis (FIA) program is required to ensure the confidentiality of the geographic locations of plots. To accommodate user requests for data without releasing actual plot coordinates, FIA creates overlays of plot locations on various geospatial data, including satellite imagery. Methods for reporting pixel values associated...

A new approach to kinetics study of the anhydrite crystallization at 373 K using a diamond anvil cell with Raman spectroscopy

NASA Astrophysics Data System (ADS)

Liu, C. J.; Zheng, H. F.

2013-04-01

A new approach to the kinetics study of anhydrite (CaSO4) crystallization has been performed in situ using a hydrothermal diamond anvil cell with Raman spectroscopy in the pressure range 896-1322 MPa and a constant temperature of 373 K. Transformed volume fraction X(t) was determined from Raman peak intensity of the sulfate ion in aqueous solution. The transformation-time plots display a sigmoidal shape with time, which indicates that the reaction rate is different at each stage of anhydrite crystallization. At 373 K, the rate constant k increases from 1.14 × 10-4 s-1 to 1.86 × 10-3 s-1, demonstrating a positive effect of pressure on the overall rate at isothermal condition. We first achieved the molar volume change (ΔVm) equal to -1.82 × 10-5 m3/mol in the course of anhydrite crystallization through Avrami kinetic theory, showing a process of reduction in volume at high pressure and high temperature. According to the exponent n derived from our experiments, a grain-boundary nucleation and diffusion-controlled growth kinetically dominates the crystallization of anhydrite.

Modeling the kinetics of survival of Staphylococcus aureus in regional yogurt from goat's milk.

PubMed

Bednarko-Młynarczyk, E; Szteyn, J; Białobrzewski, I; Wiszniewska-Łaszczych, A; Liedtke, K

2015-01-01

The aim of this study was to determine the kinetics of the survival of the test strain of Staphylococcus aureus in the product investigated. Yogurt samples were contaminated with S. aure to an initial level of 10(3)-10(4) cfu/g. The samples were then stored at four temperatures: 4, 6, 20, 22°C. During storage, the number of S. aureus forming colonies in a gram of yogurt was determined every two hours. Based on the results of the analysis culture the curves of survival were plotted. Three primary models were selected to describe the kinetics of changes in the count of bacteria: Cole's model, a modified model of Gompertz and the model of Baranyi and Roberts. Analysis of the model fit carried out based on the average values of Pearson's correlation coefficient, between the modeled and measured values, showed that the Cole's model had the worst fit. The modified Gompertz model showed the count of S. aureus as a negative value. These drawbacks were not observed in the model of Baranyi and Roberts. For this reason, this model best reflects the kinetics of changes in the number of staphylococci in yogurt.

Presenting simulation results in a nested loop plot.

PubMed

Rücker, Gerta; Schwarzer, Guido

2014-12-12

Statisticians investigate new methods in simulations to evaluate their properties for future real data applications. Results are often presented in a number of figures, e.g., Trellis plots. We had conducted a simulation study on six statistical methods for estimating the treatment effect in binary outcome meta-analyses, where selection bias (e.g., publication bias) was suspected because of apparent funnel plot asymmetry. We varied five simulation parameters: true treatment effect, extent of selection, event proportion in control group, heterogeneity parameter, and number of studies in meta-analysis. In combination, this yielded a total number of 768 scenarios. To present all results using Trellis plots, 12 figures were needed. Choosing bias as criterion of interest, we present a 'nested loop plot', a diagram type that aims to have all simulation results in one plot. The idea was to bring all scenarios into a lexicographical order and arrange them consecutively on the horizontal axis of a plot, whereas the treatment effect estimate is presented on the vertical axis. The plot illustrates how parameters simultaneously influenced the estimate. It can be combined with a Trellis plot in a so-called hybrid plot. Nested loop plots may also be applied to other criteria such as the variance of estimation. The nested loop plot, similar to a time series graph, summarizes all information about the results of a simulation study with respect to a chosen criterion in one picture and provides a suitable alternative or an addition to Trellis plots.

Field methods and data processing techniques associated with mapped inventory plots

Treesearch

William A. Bechtold; Stanley J. Zarnoch

1999-01-01

The U.S. Forest Inventory and Analysis (FIA) and Forest Health Monitoring (FHM) programs utilize a fixed-area mapped-plot design as the national standard for extensive forest inventories. The mapped-plot design is explained, as well as the rationale for its selection as the national standard. Ratio-of-means estimators am presented as a method to process data from...

A statistically valid method for using FIA plots to guide spectral class rejection in producing stratification maps

Treesearch

Michael L. Hoppus; Andrew J. Lister

2002-01-01

A Landsat TM classification method (iterative guided spectral class rejection) produced a forest cover map of southern West Virginia that provided the stratification layer for producing estimates of timberland area from Forest Service FIA ground plots using a stratified sampling technique. These same high quality and expensive FIA ground plots provided ground reference...

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

Brodde, O.E.; Leifert, F.J.; Krehl, H.J.

We determined the amount of beta 1- and beta 2-adrenoceptors in right and left atria and ventricles of rabbits. For this purpose inhibition of specific (-)-/sup 3/H-dihydroalprenolol ((-)-/sup 3/H-DHA) binding (5 nM) by beta 1-selective (practolol, metoprolol) and beta 2-selective (zinterol, IPS 339) adrenergic drugs was determined and analyzed by pseudo-Scatchard (Hofstee) plots. For both atria, inhibition of binding by the four selective beta-adrenergic drugs resulted in non-linear Hofstee plots, suggesting the coexistence of both beta-adrenoceptor subtypes. From these plots we calculated a beta 1:beta 2-adrenoceptor ratio of 72:28 for the right atrium and of 82:18 for the left. Inmore » contrast, only a very small amount of beta 2-adrenoceptors (approximately 5-7% of the total beta-adrenoceptor population) could be detected in the ventricles. For comparison we analyzed the inhibition of specific (-)-/sup 3/H-DHA binding in tissues with homogeneous population of beta-adrenoceptors (beta 1:guinea pig left ventricle; beta 2: cerebellum of mature rats). For both tissues the four selective beta-adrenergic drugs showed linear Hofstee plots, demonstrating that in tissues with homogeneous beta-receptor population interaction of each drug with the receptor followed simple mass-action kinetics. We conclude that beta 1- and beta 2-adrenoceptors coexist in rabbit atria while the ventricles are predominantly endowed the beta 1-adrenoceptors.« less

X-Ray Diffraction Profile Analysis for Characterizing Isothermal Aging Behavior of M250 Grade Maraging Steel

NASA Astrophysics Data System (ADS)

Mahadevan, S.; Jayakumar, T.; Rao, B. P. C.; Kumar, Anish; Rajkumar, K. V.; Raj, Baldev

2008-08-01

X-ray diffraction (XRD) studies were carried out to characterize aging behavior of M250 grade maraging steel samples subjected to isothermal aging at 755 K for varying durations of 0.25, 1, 3, 10, 40, 70, and 100 hours. Earlier studies had shown typical features of precipitation hardening, wherein the hardness increased to a peak value due to precipitation of intermetallics and decreased upon further aging (overaging) due to reversion of martensite to austenite. Intermetallic precipitates, while coherent, are expected to increase the microstrain in the matrix. Hence, an attempt has been made in the present study to understand the microstructural changes in these samples using XRD line profile analysis. The anisotropic broadening with diffraction angle observed in the simple Williamson Hall (WH) plot has been addressed using the modified WH (mWH) approach, which takes into account the contrast caused by dislocations on line profiles, leading to new scaling factors in the WH plot. The normalized mean square strain and crystallite size estimated from mWH have been used to infer early precipitation and to characterize aging behavior. The normalized mean square strain has been used to determine the Avrami exponent in the Johnson Mehl Avrami (JMA) equation, which deals with the kinetics of precipitation. The Avrami exponent thus determined has matched well with values found by other methods, as reported in literature.

Reversible conformational transition gives rise to 'zig-zag' temperature dependence of the rate constant of irreversible thermoinactivation of enzymes.

PubMed

Levitsky VYu; Melik-Nubarov, N S; Siksnis, V A; Grinberg VYa; Burova, T V; Levashov, A V; Mozhaev, V V

1994-01-15

We have obtained unusual 'zig-zag' temperature dependencies of the rate constant of irreversible thermoinactivation (k(in)) of enzymes (alpha-chymotrypsin, covalently modified alpha-chymotrypsin, and ribonuclease) in a plot of log k(in) versus reciprocal temperature (Arrhenius plot). These dependencies are characterized by the presence of both ascending and descending linear portions which have positive and negative values of the effective activation energy (Ea), respectively. A kinetic scheme has been suggested that fits best for a description of these zig-zag dependencies. A key element of this scheme is the temperature-dependent reversible conformational transition of enzyme from the 'low-temperature' native state to a 'high-temperature' denatured form; the latter form is significantly more stable against irreversible thermoinactivation than the native enzyme. A possible explanation for a difference in thermal stabilities is that low-temperature and high-temperature forms are inactivated according to different mechanisms. Existence of the suggested conformational transition was proved by the methods of fluorescence spectroscopy and differential scanning calorimetry. The values of delta H and delta S for this transition, determined from calorimetric experiments, are highly positive; this fact underlies a conclusion that this heat-induced transition is caused by an unfolding of the protein molecule. Surprisingly, in the unfolded high-temperature conformation, alpha-chymotrypsin has a pronounced proteolytic activity, although this activity is much smaller than that of the native enzyme.

Dispersed and piled woody residues volumes in coastal Douglas-fir cutblocks determined using high-resolution imagery from a UAV and from ground-based surveys.

NASA Astrophysics Data System (ADS)

Trofymow, J. A.; Gougeon, F.

2015-12-01

After forest harvest significant amounts of woody residues are left dispersed on site and some subsequently piled and burned. Quantification of residues is required for estimating C budgets, billable waste, harvest efficiency, bioenergy potential and smoke emissions. Trofymow (et al 2014 CJFR) compared remote sensing methods to ground-based waste and residue survey (WRS) methods for residue piles in 4 cutblocks in the Oyster River (OR) area in coastal BC. Compared to geospatial methods using 15cm orthophotos and LiDAR acquired in 2011 by helicopter, the WRS method underestimated pile wood by 30% to 50% while a USFS volume method overestimated pile wood by 50% if site specific packing ratios were not used. A geospatial method was developed in PCI Geomatica to analyze 2-bit images of logs >15cm diameters to determine dispersed wood residues in OR and compare to WRS methods. Across blocks, geospatial and WRS method wood volumes were correlated (R2=0.69), however volumes were 2.5 times larger for the geospatial vs WRS method. Methods for dispersed residues could not be properly compared as individual WRS plots were not georeferenced, only 12 plots were sampled in total, and low-resolution images poorly resolved logs. Thus, a new study in 2 cutblocks in the Northwest Bay (NWB) area acquired 2cm resolution RGB air-photography in 2014-15 using an Aeryon Sky Ranger UAV prior to and after burn pile construction. A total of 57 dispersed WRS plots and 24 WRS pile or accumulation plots were georeferenced and measured. Stero-pairs were used to generate point-clouds for pile bulk volumes. Images processed to 8-bit grey scale are being analyzed with a revised PCI method that better accounts for log overlaps. WRS methods depend on a good sample of plots and accurate determination of stratum (dispersed, roadside, piles, accumulations) areas. Analysis of NWB blocks shows WRS field methods for stratum area differ by 5-20% from that determined using orthophotos. Plot-level wood volumes in each plot and stratum determined by geospatial and WRS methods will be compared. While geospatial methods for residue determination is a 100% sample, compared to sample-based WRS method, difficulties in resolving logs in the images may mean the best method for determining residues requires a combination of geospatial and ground plot measurements. .

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

System Acquires Data On Reactivities Of Foams

NASA Technical Reports Server (NTRS)

Walls, Joe T.

1994-01-01

Data-acquisition and -plotting system, called DAPS(TM), developed enabling accurate and objective determination of physical properties related to reactivities of polyurethane and polyisocyanurate foams. Automated, computer-controlled test apparatus that acquires data on rates of rise, rise profiles, exothermic temperatures, and internal pressures of foams prepared from both manual and machine-mixed batches. Data used to determine minute differences between reaction kinetics and exothermic profiles of foam formulations, properties of end products which are statistically undifferentiated.

Relative equilibrium plot improves graphical analysis and allows bias correction of SUVR in quantitative [11C]PiB PET studies

PubMed Central

Zhou, Yun; Sojkova, Jitka; Resnick, Susan M.; Wong, Dean F.

2012-01-01

Both the standardized uptake value ratio (SUVR) and the Logan plot result in biased distribution volume ratios (DVR) in ligand-receptor dynamic PET studies. The objective of this study is to use a recently developed relative equilibrium-based graphical plot (RE plot) method to improve and simplify the two commonly used methods for quantification of [11C]PiB PET. Methods The overestimation of DVR in SUVR was analyzed theoretically using the Logan and the RE plots. A bias-corrected SUVR (bcSUVR) was derived from the RE plot. Seventy-eight [11C]PiB dynamic PET scans (66 from controls and 12 from mildly cognitively impaired participants (MCI) from the Baltimore Longitudinal Study of Aging (BLSA)) were acquired over 90 minutes. Regions of interest (ROIs) were defined on coregistered MRIs. Both the ROI and pixelwise time activity curves (TACs) were used to evaluate the estimates of DVR. DVRs obtained using the Logan plot applied to ROI TACs were used as a reference for comparison of DVR estimates. Results Results from the theoretical analysis were confirmed by human studies. ROI estimates from the RE plot and the bcSUVR were nearly identical to those from the Logan plot with ROI TACs. In contrast, ROI estimates from DVR images in frontal, temporal, parietal, cingulate regions, and the striatum were underestimated by the Logan plot (controls 4 – 12%; MCI 9 – 16%) and overestimated by the SUVR (controls 8 – 16%; MCI 16 – 24%). This bias was higher in the MCI group than in controls (p < 0.01) but was not present when data were analyzed using either the RE plot or the bcSUVR. Conclusion The RE plot improves pixel-wise quantification of [11C]PiB dynamic PET compared to the conventional Logan plot. The bcSUVR results in lower bias and higher consistency of DVR estimates compared to SUVR. The RE plot and the bcSUVR are practical quantitative approaches that improve the analysis of [11C]PiB studies. PMID:22414634

Redrawing the baseline: a method for adjusting biased historical forest estimates using a spatial and temporally representative plot network

Treesearch

Sara A. Goeking; Paul L. Patterson

2015-01-01

Users of Forest Inventory and Analysis (FIA) data sometimes compare historic and current forest inventory estimates, despite warnings that such comparisons may be tenuous. The purpose of this study was to demonstrate a method for obtaining a more accurate and representative reference dataset using data collected at co-located plots (i.e., plots that were measured...

[Application of Stata software to test heterogeneity in meta-analysis method].

PubMed

Wang, Dan; Mou, Zhen-yun; Zhai, Jun-xia; Zong, Hong-xia; Zhao, Xiao-dong

2008-07-01

To introduce the application of Stata software to heterogeneity test in meta-analysis. A data set was set up according to the example in the study, and the corresponding commands of the methods in Stata 9 software were applied to test the example. The methods used were Q-test and I2 statistic attached to the fixed effect model forest plot, H statistic and Galbraith plot. The existence of the heterogeneity among studies could be detected by Q-test and H statistic and the degree of the heterogeneity could be detected by I2 statistic. The outliers which were the sources of the heterogeneity could be spotted from the Galbraith plot. Heterogeneity test in meta-analysis can be completed by the four methods in Stata software simply and quickly. H and I2 statistics are more robust, and the outliers of the heterogeneity can be clearly seen in the Galbraith plot among the four methods.

Modules based on the geochemical model PHREEQC for use in scripting and programming languages

USGS Publications Warehouse

Charlton, Scott R.; Parkhurst, David L.

2011-01-01

The geochemical model PHREEQC is capable of simulating a wide range of equilibrium reactions between water and minerals, ion exchangers, surface complexes, solid solutions, and gases. It also has a general kinetic formulation that allows modeling of nonequilibrium mineral dissolution and precipitation, microbial reactions, decomposition of organic compounds, and other kinetic reactions. To facilitate use of these reaction capabilities in scripting languages and other models, PHREEQC has been implemented in modules that easily interface with other software. A Microsoft COM (component object model) has been implemented, which allows PHREEQC to be used by any software that can interface with a COM server—for example, Excel®, Visual Basic®, Python, or MATLAB". PHREEQC has been converted to a C++ class, which can be included in programs written in C++. The class also has been compiled in libraries for Linux and Windows that allow PHREEQC to be called from C++, C, and Fortran. A limited set of methods implements the full reaction capabilities of PHREEQC for each module. Input methods use strings or files to define reaction calculations in exactly the same formats used by PHREEQC. Output methods provide a table of user-selected model results, such as concentrations, activities, saturation indices, and densities. The PHREEQC module can add geochemical reaction capabilities to surface-water, groundwater, and watershed transport models. It is possible to store and manipulate solution compositions and reaction information for many cells within the module. In addition, the object-oriented nature of the PHREEQC modules simplifies implementation of parallel processing for reactive-transport models. The PHREEQC COM module may be used in scripting languages to fit parameters; to plot PHREEQC results for field, laboratory, or theoretical investigations; or to develop new models that include simple or complex geochemical calculations.

Modules based on the geochemical model PHREEQC for use in scripting and programming languages

USGS Publications Warehouse

Charlton, S.R.; Parkhurst, D.L.

2011-01-01

The geochemical model PHREEQC is capable of simulating a wide range of equilibrium reactions between water and minerals, ion exchangers, surface complexes, solid solutions, and gases. It also has a general kinetic formulation that allows modeling of nonequilibrium mineral dissolution and precipitation, microbial reactions, decomposition of organic compounds, and other kinetic reactions. To facilitate use of these reaction capabilities in scripting languages and other models, PHREEQC has been implemented in modules that easily interface with other software. A Microsoft COM (component object model) has been implemented, which allows PHREEQC to be used by any software that can interface with a COM server-for example, Excel??, Visual Basic??, Python, or MATLAB??. PHREEQC has been converted to a C++ class, which can be included in programs written in C++. The class also has been compiled in libraries for Linux and Windows that allow PHREEQC to be called from C++, C, and Fortran. A limited set of methods implements the full reaction capabilities of PHREEQC for each module. Input methods use strings or files to define reaction calculations in exactly the same formats used by PHREEQC. Output methods provide a table of user-selected model results, such as concentrations, activities, saturation indices, and densities. The PHREEQC module can add geochemical reaction capabilities to surface-water, groundwater, and watershed transport models. It is possible to store and manipulate solution compositions and reaction information for many cells within the module. In addition, the object-oriented nature of the PHREEQC modules simplifies implementation of parallel processing for reactive-transport models. The PHREEQC COM module may be used in scripting languages to fit parameters; to plot PHREEQC results for field, laboratory, or theoretical investigations; or to develop new models that include simple or complex geochemical calculations. ?? 2011.

Integrating P3 Data Into P2 Analyses: What is the Added Value

Treesearch

James R. Steinman

2001-01-01

The Forest Inventory and Analysis and Forest Health Monitoring Programs of the USDA Forest Service are integrating field procedures for measuring their networks of plots throughout the United States. These plots are now referred to as Phase 2 (P2) and Phase 3 (P3) plots, respectively, and 1 out of every 16 P2 plots will also be a P3 plot. Mensurational methods will be...

Computer systems and methods for visualizing data

DOEpatents

Stolte, Chris; Hanrahan, Patrick

2010-07-13

A method for forming a visual plot using a hierarchical structure of a dataset. The dataset comprises a measure and a dimension. The dimension consists of a plurality of levels. The plurality of levels form a dimension hierarchy. The visual plot is constructed based on a specification. A first level from the plurality of levels is represented by a first component of the visual plot. A second level from the plurality of levels is represented by a second component of the visual plot. The dataset is queried to retrieve data in accordance with the specification. The data includes all or a portion of the dimension and all or a portion of the measure. The visual plot is populated with the retrieved data in accordance with the specification.

Computer systems and methods for visualizing data

DOEpatents

Stolte, Chris; Hanrahan, Patrick

2013-01-29

A method for forming a visual plot using a hierarchical structure of a dataset. The dataset comprises a measure and a dimension. The dimension consists of a plurality of levels. The plurality of levels form a dimension hierarchy. The visual plot is constructed based on a specification. A first level from the plurality of levels is represented by a first component of the visual plot. A second level from the plurality of levels is represented by a second component of the visual plot. The dataset is queried to retrieve data in accordance with the specification. The data includes all or a portion of the dimension and all or a portion of the measure. The visual plot is populated with the retrieved data in accordance with the specification.

Statistical Determination of Rainfall-Runoff Erosivity Indices for Single Storms in the Chinese Loess Plateau

PubMed Central

Zheng, Mingguo; Chen, Xiaoan

2015-01-01

Correlation analysis is popular in erosion- or earth-related studies, however, few studies compare correlations on a basis of statistical testing, which should be conducted to determine the statistical significance of the observed sample difference. This study aims to statistically determine the erosivity index of single storms, which requires comparison of a large number of dependent correlations between rainfall-runoff factors and soil loss, in the Chinese Loess Plateau. Data observed at four gauging stations and five runoff experimental plots were presented. Based on the Meng’s tests, which is widely used for comparing correlations between a dependent variable and a set of independent variables, two methods were proposed. The first method removes factors that are poorly correlated with soil loss from consideration in a stepwise way, while the second method performs pairwise comparisons that are adjusted using the Bonferroni correction. Among 12 rainfall factors, I 30 (the maximum 30-minute rainfall intensity) has been suggested for use as the rainfall erosivity index, although I 30 is equally correlated with soil loss as factors of I 20, EI 10 (the product of the rainfall kinetic energy, E, and I 10), EI 20 and EI 30 are. Runoff depth (total runoff volume normalized to drainage area) is more correlated with soil loss than all other examined rainfall-runoff factors, including I 30, peak discharge and many combined factors. Moreover, sediment concentrations of major sediment-producing events are independent of all examined rainfall-runoff factors. As a result, introducing additional factors adds little to the prediction accuracy of the single factor of runoff depth. Hence, runoff depth should be the best erosivity index at scales from plots to watersheds. Our findings can facilitate predictions of soil erosion in the Loess Plateau. Our methods provide a valuable tool while determining the predictor among a number of variables in terms of correlations. PMID:25781173

Statistical determination of rainfall-runoff erosivity indices for single storms in the Chinese Loess Plateau.

PubMed

Zheng, Mingguo; Chen, Xiaoan

2015-01-01

Correlation analysis is popular in erosion- or earth-related studies, however, few studies compare correlations on a basis of statistical testing, which should be conducted to determine the statistical significance of the observed sample difference. This study aims to statistically determine the erosivity index of single storms, which requires comparison of a large number of dependent correlations between rainfall-runoff factors and soil loss, in the Chinese Loess Plateau. Data observed at four gauging stations and five runoff experimental plots were presented. Based on the Meng's tests, which is widely used for comparing correlations between a dependent variable and a set of independent variables, two methods were proposed. The first method removes factors that are poorly correlated with soil loss from consideration in a stepwise way, while the second method performs pairwise comparisons that are adjusted using the Bonferroni correction. Among 12 rainfall factors, I30 (the maximum 30-minute rainfall intensity) has been suggested for use as the rainfall erosivity index, although I30 is equally correlated with soil loss as factors of I20, EI10 (the product of the rainfall kinetic energy, E, and I10), EI20 and EI30 are. Runoff depth (total runoff volume normalized to drainage area) is more correlated with soil loss than all other examined rainfall-runoff factors, including I30, peak discharge and many combined factors. Moreover, sediment concentrations of major sediment-producing events are independent of all examined rainfall-runoff factors. As a result, introducing additional factors adds little to the prediction accuracy of the single factor of runoff depth. Hence, runoff depth should be the best erosivity index at scales from plots to watersheds. Our findings can facilitate predictions of soil erosion in the Loess Plateau. Our methods provide a valuable tool while determining the predictor among a number of variables in terms of correlations.

Evaluating Plot Designs for the Tropics

Treesearch

Paul C. van Deusen; Bruce Bayle

1991-01-01

Theory and procedures are reviewed for determining the best type of plot for a given forest inventory. A general methodology is given that clarifies the relationship between different plot designs and the associated methods to produce the inventory estimates.

Kinetic properties of wild-type and altered recombinant amidases by the use of ion-selective electrode assay method.

PubMed

Martins, S; Karmali, A; Serralheiro, M L

2006-08-15

A novel assay method was investigated for wild-type and recombinant mutant amidases (EC 3.5.1.4) from Pseudomonas aeruginosa by ammonium ion-selective electrode (ISE). The initial velocity is proportional to the enzyme concentration by using the wild-type enzyme. The specific activities of the purified amidase were found to be 88.2 and 104.2 U mg protein(-1) for the linked assay and ISE methods, respectively. The kinetic constants--Vmax, Km, and Kcat--determined by Michaelis-Menten plot were 101.13 U mg protein(-1), 1.12x10(-2) M, and 64.04 s(-1), respectively, for acrylamide as the substrate. On the other hand, the lower limit of detection and range of linearity of enzyme concentration were found to be 10.8 and 10.8 to 500 ng, respectively, for the linked assay method and 15.0 and 15.0 to 15,000 ng, respectively, for the ISE method. Hydroxylamine was found to act as an uncompetitive activator of hydrolysis reaction catalyzed by amidase given that there is an increase in Vmax and Km when acetamide was used as the substrate. However, the effect of hydroxylamine on the hydrolysis reaction was dependent on the type of amidase and substrate involved in the reaction mixture. The degrees of activation (epsilon(a)) of the wild-type and mutant (T103I and C91A) enzymes were found to be 2.54, 12.63, and 4.33, respectively, for acetamide as the substrate. However, hydroxylamine did not activate the reaction catalyzed by wild-type and altered (C91A and W138G) amidases by using acrylamide and acetamide, respectively, as the substrate. The activating effect of hydroxylamine on the hydrolysis of acetamide, acrylamide, and p-nitrophenylacetamide can be explained by the fact that additional formation of ammonium ions occurred due to the transferase activity of amidases. However, the activating effect of hydroxylamine on the hydrolysis of p-nitroacetanilide may be due to a change in conformation of enzyme molecule. Therefore, the use of ISE permitted the study of the kinetic properties of wild-type and mutant amidases because it was possible to measure initial velocity of the enzyme-catalyzed reaction in real time.

Analysis of variance calculations for irregular experiments

Treesearch

Jonathan W. Wright

1977-01-01

Irregular experiments may be more useful than much smaller regular experiments and can be analyzed statistically without undue expenditure of time. For a few missing plots, standard methods of calculating missing-plot values can be used. For more missing plots (up to 10 percent), seedlot means or randomly chosen plot means of the same seedlot can be substituted for...

Measurements of smoke from chipped and unchipped plots

Treesearch

Gary L. Achtemeier; Jeff Glitzenstein; Luke P. Naeher

2006-01-01

Smoke data were collected from two instrumented plots located on the Francis Marion National Forest in South Carolina during prescribed burns on Feb. 12, 2003. One of the plots had been subjected to mechanical chipping. Particulate matter (PM2.5) data analyzed by gravimetric methods were collected at nine locations on the downwind sides of each plot. In addition,...

Field Testing New Plot Designs and Methods for Determining Hydrophytic Vegetation during Wetland Delineations in the United States

DTIC Science & Technology

2014-03-01

Trees and woody vines are sampled in large plots with 9 m (30 ft) radii. Saplings, shrubs , and herbs are sampled in nested smaller plots with 2 m (5 ft... woody vines in 9 m (30 ft) radius plots and saplings, shrubs , and herbaceous species in 2 m (5 ft) radius plots. In herbaceous meadows, only the 2 m (5...suggests stratifying vegetation by growth forms of trees, shrubs , herbs, and vines and sampling plant communities by using nested circular plots

[Study on extraction method of Panax notoginseng plots in Wenshan of Yunnan province based on decision tree model].

PubMed

Shi, Ting-Ting; Zhang, Xiao-Bo; Guo, Lan-Ping; Huang, Lu-Qi

2017-11-01

The herbs used as the material for traditional Chinese medicine are always planted in the mountainous area where the natural environment is suitable. As the mountain terrain is complex and the distribution of planting plots is scattered, the traditional survey method is difficult to obtain accurate planting area. It is of great significance to provide decision support for the conservation and utilization of traditional Chinese medicine resources by studying the method of extraction of Chinese herbal medicine planting area based on remote sensing and realizing the dynamic monitoring and reserve estimation of Chinese herbal medicines. In this paper, taking the Panax notoginseng plots in Wenshan prefecture of Yunnan province as an example, the China-made GF-1multispectral remote sensing images with a 16 m×16 m resolution were obtained. Then, the time series that can reflect the difference of spectrum of P. notoginseng shed and the background objects were selected to the maximum extent, and the decision tree model of extraction the of P. notoginseng plots was constructed according to the spectral characteristics of the surface features. The results showed that the remote sensing classification method based on the decision tree model could extract P. notoginseng plots in the study area effectively. The method can provide technical support for extraction of P. notoginseng plots at county level. Copyright© by the Chinese Pharmaceutical Association.

What is the best method for assessing lower limb force-velocity relationship?

PubMed

Giroux, C; Rabita, G; Chollet, D; Guilhem, G

2015-02-01

This study determined the concurrent validity and reliability of force, velocity and power measurements provided by accelerometry, linear position transducer and Samozino's methods, during loaded squat jumps. 17 subjects performed squat jumps on 2 separate occasions in 7 loading conditions (0-60% of the maximal concentric load). Force, velocity and power patterns were averaged over the push-off phase using accelerometry, linear position transducer and a method based on key positions measurements during squat jump, and compared to force plate measurements. Concurrent validity analyses indicated very good agreement with the reference method (CV=6.4-14.5%). Force, velocity and power patterns comparison confirmed the agreement with slight differences for high-velocity movements. The validity of measurements was equivalent for all tested methods (r=0.87-0.98). Bland-Altman plots showed a lower agreement for velocity and power compared to force. Mean force, velocity and power were reliable for all methods (ICC=0.84-0.99), especially for Samozino's method (CV=2.7-8.6%). Our findings showed that present methods are valid and reliable in different loading conditions and permit between-session comparisons and characterization of training-induced effects. While linear position transducer and accelerometer allow for examining the whole time-course of kinetic patterns, Samozino's method benefits from a better reliability and ease of processing. © Georg Thieme Verlag KG Stuttgart · New York.

In-situ polymerization PLOT columns I: divinylbenzene

NASA Technical Reports Server (NTRS)

Shen, T. C.

1992-01-01

A novel method for preparation of porous-layer open-tubular (PLOT) columns is described. The method involves a simple and reproducible, straight-forward in-situ polymerization of monomer directly on the metal tube.

Investigation of ODE integrators using interactive graphics. [Ordinary Differential Equations

NASA Technical Reports Server (NTRS)

Brown, R. L.

1978-01-01

Two FORTRAN programs using an interactive graphic terminal to generate accuracy and stability plots for given multistep ordinary differential equation (ODE) integrators are described. The first treats the fixed stepsize linear case with complex variable solutions, and generates plots to show accuracy and error response to step driving function of a numerical solution, as well as the linear stability region. The second generates an analog to the stability region for classes of non-linear ODE's as well as accuracy plots. Both systems can compute method coefficients from a simple specification of the method. Example plots are given.

Evaluation of a new inference method for estimating ammonia volatilisation from multiple agronomic plots

NASA Astrophysics Data System (ADS)

Loubet, Benjamin; Carozzi, Marco; Voylokov, Polina; Cohan, Jean-Pierre; Trochard, Robert; Génermont, Sophie

2018-06-01

Tropospheric ammonia (NH3) is a threat to the environment and human health and is mainly emitted by agriculture. Ammonia volatilisation following application of nitrogen in the field accounts for more than 40 % of the total NH3 emissions in France. This represents a major loss of nitrogen use efficiency which needs to be reduced by appropriate agricultural practices. In this study we evaluate a novel method to infer NH3 volatilisation from small agronomic plots consisting of multiple treatments with repetition. The method is based on the combination of a set of NH3 diffusion sensors exposed for durations of 3 h to 1 week and a short-range atmospheric dispersion model, used to retrieve the emissions from each plot. The method is evaluated by mimicking NH3 emissions from an ensemble of nine plots with a resistance analogue-compensation point-surface exchange scheme over a yearly meteorological database separated into 28-day periods. A multifactorial simulation scheme is used to test the effects of sensor numbers and heights, plot dimensions, source strengths, and background concentrations on the quality of the inference method. We further demonstrate by theoretical considerations in the case of an isolated plot that inferring emissions with diffusion sensors integrating over daily periods will always lead to underestimations due to correlations between emissions and atmospheric transfer. We evaluated these underestimations as -8 % ± 6 % of the emissions for a typical western European climate. For multiple plots, we find that this method would lead to median underestimations of -16 % with an interquartile [-8-22 %] for two treatments differing by a factor of up to 20 and a control treatment with no emissions. We further evaluate the methodology for varying background concentrations and NH3 emissions patterns and demonstrate the low sensitivity of the method to these factors. The method was also tested in a real case and proved to provide sound evaluations of NH3 losses from surface applied and incorporated slurry. We hence showed that this novel method should be robust and suitable for estimating NH3 emissions from agronomic plots. We believe that the method could be further improved by using Bayesian inference and inferring surface concentrations rather than surface fluxes. Validating against controlled source is also a remaining challenge.

The role of the C-domain of bacteriophage T4 gene 32 protein in ssDNA binding and dsDNA helix-destabilization: Kinetic, single-molecule, and cross-linking studies

PubMed Central

Pant, Kiran; Anderson, Brian; Perdana, Hendrik; Malinowski, Matthew A.; Win, Aye T.; Williams, Mark C.

2018-01-01

The model single-stranded DNA binding protein of bacteriophage T4, gene 32 protein (gp32) has well-established roles in DNA replication, recombination, and repair. gp32 is a single-chain polypeptide consisting of three domains. Based on thermodynamics and kinetics measurements, we have proposed that gp32 can undergo a conformational change where the acidic C-terminal domain binds internally to or near the single-stranded (ss) DNA binding surface in the core (central) domain, blocking ssDNA interaction. To test this model, we have employed a variety of experimental approaches and gp32 variants to characterize this conformational change. Utilizing stopped-flow methods, the association kinetics of wild type and truncated forms of gp32 with ssDNA were measured. When the C-domain is present, the log-log plot of k vs. [NaCl] shows a positive slope, whereas when it is absent (*I protein), there is little rate change with salt concentration, as expected for this model.A gp32 variant lacking residues 292–296 within the C-domain, ΔPR201, displays kinetic properties intermediate between gp32 and *I. The single molecule force-induced DNA helix-destabilizing activitiesas well as the single- and double-stranded DNA affinities of ΔPR201 and gp32 truncated at residue 295 also fall between full-length protein and *I. Finally, chemical cross-linking of recombinant C-domain and gp32 lacking both N- and C-terminal domains is inhibited by increasing concentrations of a short single-stranded oligonucleotide, and the salt dependence of cross-linking mirrors that expected for the model. Taken together, these results provide the first evidence in support of this model that have been obtained through structural probes. PMID:29634784

Convergence optimization of parametric MLEM reconstruction for estimation of Patlak plot parameters.

PubMed

Angelis, Georgios I; Thielemans, Kris; Tziortzi, Andri C; Turkheimer, Federico E; Tsoumpas, Charalampos

2011-07-01

In dynamic positron emission tomography data many researchers have attempted to exploit kinetic models within reconstruction such that parametric images are estimated directly from measurements. This work studies a direct parametric maximum likelihood expectation maximization algorithm applied to [(18)F]DOPA data using reference-tissue input function. We use a modified version for direct reconstruction with a gradually descending scheme of subsets (i.e. 18-6-1) initialized with the FBP parametric image for faster convergence and higher accuracy. The results compared with analytic reconstructions show quantitative robustness (i.e. minimal bias) and clinical reproducibility within six human acquisitions in the region of clinical interest. Bland-Altman plots for all the studies showed sufficient quantitative agreement between the direct reconstructed parametric maps and the indirect FBP (--0.035x+0.48E--5). Copyright © 2011 Elsevier Ltd. All rights reserved.

Analysis of arson fire debris by low temperature dynamic headspace adsorption porous layer open tubular columns.

PubMed

Nichols, Jessica E; Harries, Megan E; Lovestead, Tara M; Bruno, Thomas J

2014-03-21

In this paper we present results of the application of PLOT-cryoadsorption (PLOT-cryo) to the analysis of ignitable liquids in fire debris. We tested ignitable liquids, broadly divided into fuels and solvents (although the majority of the results presented here were obtained with gasoline and diesel fuel) on three substrates: Douglas fir, oak plywood and Nylon carpet. We determined that PLOT-cryo allows the analyst to distinguish all of the ignitable liquids tested by use of a very rapid sampling protocol, and performs better (more recovered components, higher efficiency, lower elution solvent volumes) than a conventional purge and trap method. We also tested the effect of latency (the time period between applying the ignitable liquid and ignition), and we tested a variety of sampling times and a variety of PLOT capillary lengths. Reliable results can be obtained with sampling time periods as short as 3min, and on PLOT capillaries as short as 20cm. The variability of separate samples was also assessed, a study made possible by the high throughput nature of the PLOT-cryo method. We also determined that the method performs better than the conventional carbon strip method that is commonly used in fire debris analysis. Published by Elsevier B.V.

Simulated glass transition of poly(ethylene oxide) bulk and film: a comparative study.

PubMed

Wu, Chaofu

2011-09-29

Stepwise cooling molecular dynamics (MD) simulations have been carried out on the bulk and film models for poly(ethylene oxide) (PEO) to understand glass transition of amorphous polymer films. Three types of properties--density, energy, and dynamics--are computed and plotted against the temperature for the two systems. It has been confirmed that all these properties can reveal glass transition in both PEO bulk and film systems. All the determined glass transition temperatures (T(g)'s) drop in the same order of magnitude to the experimental data available. Among various methods, the T(g)'s obtained from the density and energy data are close to each other if the same space regions are defined, which can suggest the same free volume theory, and dynamic T(g)'s obtained from mean-squared displacements (MSDs) are highest, which can suggest the kinetic theory for structural relaxation. Consistently, all these T(g)'s obtained using different methods show that the T(g)'s of PEO film are lower than those of PEO bulk. The free surface layers of polymer films dictate this offset. © 2011 American Chemical Society

[Recurrence plot analysis of HRV for brain ischemia and asphyxia].

PubMed

Chen, Xiaoming; Qiu, Yihong; Zhu, Yisheng

2008-02-01

Heart rate variability (HRV) is the tiny variability existing in the cycles of the heart beats, which reflects the corresponding balance between sympathetic and vagus nerves. Since the nonlinear characteristic of HRV is confirmed, the Recurrence Plot method, a nonlinear dynamic analysis method based on the complexity, could be used to analyze HRV. The results showed the recurrence plot structures and some quantitative indices (L-Mean, L-Entr) during asphyxia insult vary significantly as compared to those in normal conditions, which offer a new method to monitor brain asphyxia injury.

Variable-temperature Fourier transform near-infrared imaging spectroscopy of the deuterium/hydrogen exchange in liquid D₂O.

PubMed

Unger, Miriam; Ozaki, Yukihiro; Siesler, Heinz W

2014-01-01

In the present publication, the deuterium/hydrogen (D/H) exchange of liquid D2O exposed to water vapor of the surrounding atmosphere has been studied by variable-temperature Fourier transform near-infrared (FT-NIR) imaging spectroscopy. Apart from the visualization of the exchange process in the time-resolved FT-NIR images, kinetic parameters and the activation energy for this D/H exchange reaction have been derived from the Arrhenius plot of the variable-temperature spectroscopic data.

Stoichiometry of maltodextrin-binding sites in LamB, an outer membrane protein from Escherichia coli.

PubMed Central

Gehring, K; Cheng, C H; Nikaido, H; Jap, B K

1991-01-01

We have directly measured the stoichiometry of maltodextrin-binding sites in LamB. Scatchard plots and computer fitting of flow dialysis (rate-of-dialysis) experiments clearly establish three independent binding sites per LamB trimer, with a dissociation constant of approximately 60 microM for maltoheptaose. The current model for LamB's function as a specific pore is discussed with respect to the symmetry in LamB's kinetic properties and the implications of our results. Images PMID:2001992

Formation of Monolayer Films by the Spontaneous Assembly of Organic Thiols from Solution onto Gold

DTIC Science & Technology

1988-09-01

we estimated a theoretical slope of 1.27 A per CH2 unit and an intercept of 4 A. The dashed line represents the thickness expected for a monolayer...a scale of only a few hundred angstroms--well below the length scale expected theoretically to give rise to hysteresis.31 ,78 Figure 4 plots contact... photoionization cross-sections calculated by Scofield117 , corrected for the dependence of the escape depth on the kinetic energy of the electrons (assumed to have

Formation of bisphenol A by thermal degradation of poly(bisphenol A carbonate).

PubMed

Kitahara, Yuki; Takahashi, Seiji; Tsukagoshi, Masamichi; Fujii, Toshihiro

2010-09-01

The thermal decomposition of poly(bisphenol A carbonate) (PoC) results in the formation of the endocrine disruptor bisphenol A (BPA). In the present work, we investigated the kinetics of the thermal decomposition of PoC, and the subsequent decomposition of BPA, under pyrolysis conditions and in the presence of oxygen by using infrared image furnace-ion attachment mass spectrometry. The decomposition of PoC obeyed Arrhenius kinetics, which allowed us to determine the activation energy (E(a)) for thermal decomposition to BPA from Arrhenius plots. From the selected ion monitoring curves for BPA, E(a) for thermal decomposition in a nitrogen atmosphere was calculated to be 133.2 kcal mol(-1), whereas E(a) for oxidative thermal decomposition was calculated to be approximately 35% lower (86.5 kcal mol(-1)). Copyright (c) 2010 Elsevier Ltd. All rights reserved.

A new method for the preparation of polymeric porous layer open tubular columns for GC application

NASA Technical Reports Server (NTRS)

Shen, T. C.; Wang, M. L.

1995-01-01

A new method to prepare polymeric PLOT columns by using in situ polymerization technology is described. The method involves a straightforward in situ polymerization of the monomer. The polymer produced is directly coated on the metal tubing. This eliminates many of the steps needed in conventional polymeric PLOT column preparation. Our method is easy to operate and produces very reproducible columns, as shown previously (T. C. Shen. J. Chromatogr. Sci. 30, 239, 1992). The effects of solvents, tubing pretreatments, initiators and reaction temperatures in the preparation of PLOT columns are studied. Several columns have been developed to separate (1) highly polar compounds, such as water and ammonia or water and HCN, and (2) hydrocarbons and inert gases. A recent improvement has allowed us to produce bonded polymeric PLOT columns. These were studied, and the results are included also.

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.

New methods, algorithms, and software for rapid mapping of tree positions in coordinate forest plots

Treesearch

A. Dan Wilson

2000-01-01

The theories and methodologies for two new tree mapping methods, the Sequential-target method and the Plot-origin radial method, are described. The methods accommodate the use of any conventional distance measuring device and compass to collect horizontal distance and azimuth data between source or reference positions (origins) and target trees. Conversion equations...

Hydrogenation properties of KSi and NaSi Zintl phases.

PubMed

Tang, Wan Si; Chotard, Jean-Noël; Raybaud, Pascal; Janot, Raphaël

2012-10-14

The recently reported KSi-KSiH(3) system can store 4.3 wt% of hydrogen reversibly with slow kinetics of several hours for complete absorption at 373 K and complete desorption at 473 K. From the kinetics measured at different temperatures, the Arrhenius plots give activation energies (E(a)) of 56.0 ± 5.7 kJ mol(-1) and 121 ± 17 kJ mol(-1) for the absorption and desorption processes, respectively. Ball-milling with 10 wt% of carbon strongly improves the kinetics of the system, i.e. specifically the initial rate of absorption becomes about one order of magnitude faster than that of pristine KSi. However, this fast absorption causes a disproportionation into KH and K(8)Si(46), instead of forming the KSiH(3) hydride from a slow absorption. This disproportionation, due to the formation of stable KH, leads to a total loss of reversibility. In a similar situation, when the pristine Zintl NaSi phase absorbs hydrogen, it likewise disproportionates into NaH and Na(8)Si(46), indicating a very poorly reversible reaction.

Preliminary investigation of the kinetics of primary creep of a two phase gamma TiAl alloy

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

Hayes, R.W.

1993-11-01

It is the intent of this communication to present and discuss some data regarding the kinetics of primary creep of a two phase gamma TiAl alloy which had been studied previously to determine the mechanisms giving rise to the minimum strain rate. In order to study the kinetics of primary creep of the present gamma TiAl alloy an approach previously taken by Dorn et al and also recently employed by Argon and Bhattacharya was taken. Dorn et al demonstrated that at a given constant stress, the strain rate during primary creep is governed by a combined time-temperature parameter [Theta] =more » t exp([minus]Q/RT) where Q is the activation energy for self diffusion which many times also governs the process of steady-state creep. It was shown that at the same constant stress level all primary creep curves were found to collapse on one another when the primary creep strain is plotted as a function of [Theta][sup (9)].« less

Empirical kinetics and their role in elucidating the utility of transition-state theory to mineral–water reactions. A comment upon, ''Evidence and Potential Implications of Exponential Tails to Concentration Versus Time Plots for the Batch Dissolution of Calcite'' by V. W. Truesdale

DOE PAGES

Icenhower, Jonathan P.

2015-06-23

Transition-state theory (TST) is a successful theory for understanding many different types of reactions, but its application to mineral-water systems has not been successful, especially as the system approaches saturation with respect to a rate-limiting phase. A number of investigators have proposed alternate frameworks for using the kinetic rate data to construct models of dissolution, including Truesdale (Aquat Geochem, 2015; this issue). This alternate approach has been resisted, in spite of self-evident discrepancies between TST expectations and the data. The failure of TST under certain circumstances is a result of the presence of metastable intermediaries or reaction layers that formmore » on the surface of reacting solids, and these phenomena are not anticipated by the current theory. Furthermore, alternate approaches, such as the shrinking object model advocated by Truesdale, represent a potentially important avenue for advancing the science of dissolution kinetics.« less

Drug Resistance and the Kinetics of Metastatic Cancer

NASA Astrophysics Data System (ADS)

Blagoev, Krastan B.

2012-02-01

Most metastatic cancers after initial response to current drug therapies develop resistance to the treatment. We present cancer data and a theory that explains the observed kinetics of tumor growth in cancer patients and using a stochastic model based on this theory we relate the kinetics of tumor growth to Kaplan-Meyer survival curves. The theory points to the tumor growth rate as the most important parameter determining the outcome of a drug treatment. The overall tumor growth or decay rate is a reflection of the balance between cell division, senescence and apoptosis and we propose that the deviation of the decay rate from exponential is a measure of the emergence of drug resistance. In clinical trials the progression free survival, the overall survival, and the shape of the Kaplan-Meyer plots are determined by the tumor growth rate probability distribution among the patients in the trial. How drug treatments modify this distribution will also be described. At the end of the talk we will discuss the connection between the theory described here and the age related cancer mortality rates in the United States.

Hypouricaemic action of mangiferin results from metabolite norathyriol via inhibiting xanthine oxidase activity.

PubMed

Niu, Yanfen; Liu, Jia; Liu, Hai-Yang; Gao, Li-Hui; Feng, Guo-Hua; Liu, Xu; Li, Ling

2016-09-01

Context Mangiferin has been reported to possess a potential hypouricaemic effect. However, the pharmacokinetic studies in rats showed that its oral bioavailability was only 1.2%, suggesting that mangiferin metabolites might exert the action. Objective The hypouricaemic effect and the xanthine oxidase inhibition of mangiferin and norathyriol, a mangiferin metabolite, were investigated. Inhibition of norathyriol analogues (compounds 3-9) toward xanthine oxidase was also evaluated. Materials and methods For a dose-dependent study, mangiferin (1.5-6.0 mg/kg) and norathyriol (0.92-3.7 mg/kg) were administered intragastrically to mice twice daily for five times. For a time-course study, mice received mangiferin and norathyriol both at a single dose of 7.1 μmol/kg. In vitro, inhibition of test compounds (2.4-2.4 mM) against xanthine oxidase activity was evaluated by the spectrophotometrical method. The inhibition type was identified from Lineweaver-Burk plots. Results Norathyriol (0.92, 1.85 and 3.7 mg/kg) dose dependently decreased the serum urate levels by 27.0, 33.6 and 37.4%, respectively. The action was more potent than that of mangiferin at the low dose, but was equivalent at the higher doses. Additionally, the hypouricaemic action of them exhibited a time dependence. In vitro, norathyriol markedly inhibited the xanthine oxidase activities, with the IC50 value of 44.6 μM, but mangiferin did not. The kinetic studies showed that norathyriol was an uncompetitive inhibitor by Lineweaver-Burk plots. The structure-activity relationships exhibited that three hydroxyl groups in norathyriol at the C-1, C-3 and C-6 positions were essential for maintaining xanthine oxidase inhibition. Discussion and conclusion Norathyriol was responsible for the hypouricaemic effect of mangiferin via inhibiting xanthine oxidase activity.

Measuring larval nematode contamination on cattle pastures: Comparing two herbage sampling methods.

PubMed

Verschave, S H; Levecke, B; Duchateau, L; Vercruysse, J; Charlier, J

2015-06-15

Assessing levels of pasture larval contamination is frequently used to study the population dynamics of the free-living stages of parasitic nematodes of livestock. Direct quantification of infective larvae (L3) on herbage is the most applied method to measure pasture larval contamination. However, herbage collection remains labour intensive and there is a lack of studies addressing the variation induced by the sampling method and the required sample size. The aim of this study was (1) to compare two different sampling methods in terms of pasture larval count results and time required to sample, (2) to assess the amount of variation in larval counts at the level of sample plot, pasture and season, respectively and (3) to calculate the required sample size to assess pasture larval contamination with a predefined precision using random plots across pasture. Eight young stock pastures of different commercial dairy herds were sampled in three consecutive seasons during the grazing season (spring, summer and autumn). On each pasture, herbage samples were collected through both a double-crossed W-transect with samples taken every 10 steps (method 1) and four random located plots of 0.16 m(2) with collection of all herbage within the plot (method 2). The average (± standard deviation (SD)) pasture larval contamination using sampling methods 1 and 2 was 325 (± 479) and 305 (± 444)L3/kg dry herbage (DH), respectively. Large discrepancies in pasture larval counts of the same pasture and season were often seen between methods, but no significant difference (P = 0.38) in larval counts between methods was found. Less time was required to collect samples with method 2. This difference in collection time between methods was most pronounced for pastures with a surface area larger than 1 ha. The variation in pasture larval counts from samples generated by random plot sampling was mainly due to the repeated measurements on the same pasture in the same season (residual variance component = 6.2), rather than due to pasture (variance component = 0.55) or season (variance component = 0.15). Using the observed distribution of L3, the required sample size (i.e. number of plots per pasture) for sampling a pasture through random plots with a particular precision was simulated. A higher relative precision was acquired when estimating PLC on pastures with a high larval contamination and a low level of aggregation compared to pastures with a low larval contamination when the same sample size was applied. In the future, herbage sampling through random plots across pasture (method 2) seems a promising method to develop further as no significant difference in counts between the methods was found and this method was less time consuming. Copyright © 2015 Elsevier B.V. All rights reserved.

Adsorptive removal of dissolved organic matter (DOM) in landfill leachate by iron oxide nanoparticles (FeONPs)

NASA Astrophysics Data System (ADS)

Ghani, Zaidi Ab; Yusoff, Mohd Suffian; Zaman, Nastaein Qamaruz; Andas, Jeyashelly; Aziz, Hamidi Abdul

2017-10-01

A study was conducted to investigate the efficiency of iron oxide nanoparticle (FeONPs) adsorption for removing of DOM in landfill leachate. FeONPs was directly prepared via sodium borohydride (KBH4) reduction method. Adsorption kinetics, isotherm and thermodynamic studies were developed to design the model for DOM removal. Pseudo first-order and pseudo second-order model have been studied to fit the experimental data. The regression results showed that the adsorption kinetics were more accurately represented by a pseudo second-order model. The Weber-Morris intraparticle diffusion model was used to analyze the adsorption kinetics data. The plot of qt versus t1/2 represents multi linearity, which showed that the adsorption processes occurred in more than one step. Adsorption isotherms were analyzed by Langmuir, Freundlich, Tempkin and Dubinin-Radushkevich, isotherms model. Equilibrium data were well fitted to the Dubinin- Radushkevich isotherm model. Maximum monolayer adsorption based on Langmuir was calculated to be 21.74 mg/g. Thermodynamic parameters such as free energy changes (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) were evaluated between temperatures of 25 °C and 40 °C. The ΔG° was noticed progressively decrease from -9.620 -9.820 -10.021, and -10.222 kJ/mol as the temperature increase. The ΔH° and ΔS° values were found to be 2.350 kJ/mol and 40.165 J/mol.K respectively. The results showed that the overall adsorption process was endothermic and spontaneous. The results from this study suggested that FeNPs could be a viable adsorbent in managing higher DOM problems associated with landfill leachate.

Detection and monitoring of invasive exotic plants: a comparison of four sampling methods

Treesearch

Cynthia D. Huebner

2007-01-01

The ability to detect and monitor exotic invasive plants is likely to vary depending on the sampling method employed. Methods with strong qualitative thoroughness for species detection often lack the intensity necessary to monitor vegetation change. Four sampling methods (systematic plot, stratified-random plot, modified Whittaker, and timed meander) in hemlock and red...

On fixed-area plot sampling for downed coarse woody debris

Treesearch

Jeffrey H. Gove; Paul C. Van Deusen

2011-01-01

The use of fixed-area plots for sampling down coarse woody debris is reviewed. A set of clearly defined protocols for two previously described methods is established and a new method, which we call the 'sausage' method, is developed. All methods (protocols) are shown to be unbiased for volume estimation, but not necessarily for estimation of population...

Partitioning soil respiration: examining the artifacts of the trenching method.

NASA Astrophysics Data System (ADS)

Savage, K. E.; Davidson, E. A.; Finzi, A.; Giasson, M. A.; Wehr, R. A.

2014-12-01

Soil respiration (Rs) is a combination of autotrophic (Ra) and heterotrophic respiration (Rh). Several methods have been developed to tease out the components of Rs, such as isotopic analyses, and removing Ra input through tree girdling and root exclusion experiments. Trenching involves severing the rooting system surrounding a plot to remove the Ra component within the plot. This method has some potential limitations. Reduced water uptake in trenched plots could change soil water content, which is one of the environmental controllers of Rs in many ecosystems. Eliminating root inputs could reduce heterotrophic decomposition of SOM via lack of priming. On the other hand, the severed dead roots may temporarily increase available carbon substrate for Rh. At the Harvard Forest, MA, we used the trenching method to partition Rs into its components Ra and Rh. Pre-trenched Rs was measured from spring to fall of 2012. In late fall of 2012, a trench was excavated to 1m depth around a 5x5m area, severing all roots. Plastic tarp was placed along the trench walls and then backfilled. Four automated Rs chambers were placed in the trenched plot and four in an un-trenched plot. Respiration was measured hourly for each chamber along with soil temperature and moisture from spring through fall of 2013 and 2014. Eighty root decomposition bags were placed in the organic soil horizon of the trenched (40) and un-trenched (40) plots at the time of trenching in 2012 and measured in 2013 and 2014. These data are being used to estimate the size and duration of any artifact due to root death. As expected, Rs was lower in the trenched plot (Rh only) than in the un-trenched plot (Rh + Ra) in 2013, but the reverse was unexpectedly observed during a period of low precipitation in 2014. High rates of ET combined with below-average precipitation dried the un-trenched plot to a point where Rh was inhibited, whereas less ET allowed the un-trenched plots to remain measurably wetter.

Kinetically-Defined Component Actions in Gene Repression

PubMed Central

Chow, Carson C.; Finn, Kelsey K.; Storchan, Geoffery B.; Lu, Xinping; Sheng, Xiaoyan; Simons, S. Stoney

2015-01-01

Gene repression by transcription factors, and glucocorticoid receptors (GR) in particular, is a critical, but poorly understood, physiological response. Among the many unresolved questions is the difference between GR regulated induction and repression, and whether transcription cofactor action is the same in both. Because activity classifications based on changes in gene product level are mechanistically uninformative, we present a theory for gene repression in which the mechanisms of factor action are defined kinetically and are consistent for both gene repression and induction. The theory is generally applicable and amenable to predictions if the dose-response curve for gene repression is non-cooperative with a unit Hill coefficient, which is observed for GR-regulated repression of AP1LUC reporter induction by phorbol myristate acetate. The theory predicts the mechanism of GR and cofactors, and where they act with respect to each other, based on how each cofactor alters the plots of various kinetic parameters vs. cofactor. We show that the kinetically-defined mechanism of action of each of four factors (reporter gene, p160 coactivator TIF2, and two pharmaceuticals [NU6027 and phenanthroline]) is the same in GR-regulated repression and induction. What differs is the position of GR action. This insight should simplify clinical efforts to differentially modulate factor actions in gene induction vs. gene repression. PMID:25816223

Stability-indicating spectrofluorimetric method for determination of itopride hydrochloride in raw material and pharmaceutical formulations.

PubMed

Walash, Mohamed I; Ibrahim, Fawzia; Eid, Manal I; El Abass, Samah Abo

2013-11-01

A simple, sensitive and rapid spectrofluorimetric method for determination of itopride hydrochloride in raw material and tablets has been developed. The proposed method is based on the measurement of the native fluorescence of the drug in water at 363 nm after excitation at 255 nm. The relative fluorescence intensity-concentration plot was rectilinear over the range of 0.1-2 μg/mL (2.5 × 10(-7)-5.06 × 10(-6) mole/L), with good correlation (r = 0.9999), limit of detection of 0.015 μg/mL and a lower limit of quantification of 0.045 μg/mL. The described method was successfully applied for the determination of itopride hydrochloride in its commercial tablets with average percentage recovery of 100.11 ± 0.32 without interference from common excipients. Additionally, the proposed method can be applied for determination of itopride in combined tablets with rabeprazole or pantoprazole without prior separation. The method was extended to stability study of itopride. The drug was exposed to acidic, alkaline, oxidative and photolytic degradation according to ICH guidelines. Moreover, the method was utilized to investigate the kinetics of the alkaline, acidic and oxidative degradation of the drug. A proposal for the degradation pathways was postulated.

Dissipation of the fungicide hexaconazole in oil palm plantation.

PubMed

Maznah, Zainol; Halimah, Muhamad; Ismail, Sahid; Idris, Abu Seman

2015-12-01

Hexaconazole is a potential fungicide to be used in the oil palm plantation for controlling the basal stem root (BSR) disease caused by Ganoderma boninense. Therefore, the dissipation rate of hexaconazole in an oil palm agroecosystem under field conditions was studied. Two experimental plots were treated with hexaconazole at the recommended dosage of 4.5 g a.i. palm(-1) (active ingredient) and at double the recommended dosage (9.0 g a.i. palm(-1)), whilst one plot was untreated as control. The residue of hexaconazole was detected in soil samples in the range of 2.74 to 0.78 and 7.13 to 1.66 mg kg(-1) at the recommended and double recommended dosage plots, respectively. An initial relatively rapid dissipation rate of hexaconazole residues occurred but reduced with time. The dissipation of hexaconazole in soil was described using first-order kinetics with the value of coefficient regression (r (2) > 0.8). The results indicated that hexaconazole has moderate persistence in the soil and the half-life was found to be 69.3 and 86.6 days in the recommended and double recommended dosage plot, respectively. The results obtained highlight that downward movement of hexaconazole was led by preferential flow as shown in image analysis. It can be concluded that varying soil conditions, environmental factors, and pesticide chemical properties of hexaconazole has a significant impact on dissipation of hexaconazole in soil under humid conditions.

Dissipation and runoff transport of metazachlor herbicide in rapeseed cultivated and uncultivated plots in field conditions.

PubMed

Mantzos, Nikolaos; Hela, Dimitra; Karakitsou, Anastasia; Antonopoulou, Maria; Konstantinou, Ioannis

2016-10-01

The environmental fate of metazachlor herbicide was investigated under field conditions in rapeseed cultivated and uncultivated plots, over a period of 225 days. The cultivation was carried out in silty clay soil plots with two surface slopes, 1 and 5 %. The herbicide was detectable in soil up to 170 days after application (DAA), while the dissipation rate was best described by first-order kinetics and its half-life ranged between 10.92 and 12.68 days. The herbicide was detected in the soil layer of 10-20 cm from 5 to 48 DAA, and its vertical movement can be described by the continuous stirred tank reactor (CSTR) in series model. Relatively low amounts of metazachlor (less than 0.31 % of the initial applied active ingredient) were transferred by runoff water. More than 80 % of the total losses were transferred at the first runoff event (12 DAA), with herbicide concentrations in runoff water ranging between 70.14 and 79.67 μg L -1 . Minor amounts of the herbicide (less than 0.07 % of the initial applied active ingredient) were transferred by the sediment, with a maximum concentration of 0.57 μg g -1 (12 DAA), in plots with 5 % inclination. Finally, in rapeseed plants, metazachlor was detected only in the first sampling (28 DAA) at concentrations slightly higher than the limit of quantification; when in seeds, no residues of the herbicide were detected.

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.

A kinetic study on sesame cake protein hydrolysis by Alcalase.

PubMed

Demirhan, Elçin; Apar, Dilek Kılıç; Özbek, Belma

2011-01-01

In the present study, the hydrolysis of sesame cake protein was performed by Alcalase, a bacterial protease produced by Bacillus licheniformis, to investigate the reaction kinetics of sesame cake hydrolysis and to determine decay and product inhibition effects for Alcalase. The reactions were carried out for 10 min in 0.1 L of aqueous solutions containing 10, 15, 20, 25, and 30 g protein/L at various temperature and pH values. To determine decay and product inhibition effects for Alcalase, a series of inhibition experiments were conducted with the addition of various amounts of hydrolysate. The reaction kinetics was investigated by initial rate approach. The initial reaction rates were determined from the slopes of the linear models that fitted to the experimental data. The kinetic parameters, K(m) and V(max), were estimated as 41.17 g/L and 9.24 meqv/L x min. The Lineweaver-Burk plots showed that the type of inhibition for Alcalase determined as uncompetitive, and the inhibition constant, K(i), was estimated as 38.24% (hydrolysate/substrate mixture). Practical Application: Plant proteins are increasingly being used as an alternative to proteins from animal sources to perform functional roles in food formulation. Knowledge of the kinetics of the hydrolysis reaction is essential for the optimization of enzymatic protein hydrolysis and for increasing the utilization of plant proteins in food products. Therefore, in the present study, the hydrolysis of sesame cake protein was performed by Alcalase, a bacterial protease produced by B. licheniformis, to investigate the reaction kinetics of sesame cake hydrolysis and to determine decay and product inhibition effects for Alcalase.

Hot prominence detected in the core of a coronal mass ejection. II. Analysis of the C III line detected by SOHO/UVCS

NASA Astrophysics Data System (ADS)

Jejčič, S.; Susino, R.; Heinzel, P.; Dzifčáková, E.; Bemporad, A.; Anzer, U.

2017-11-01

Context. We study the physics of erupting prominences in the core of coronal mass ejections (CMEs) and present a continuation of a previous analysis. Aims: We determine the kinetic temperature and microturbulent velocity of an erupting prominence embedded in the core of a CME that occurred on August 2, 2000 using the Ultraviolet Coronagraph and Spectrometer observations (UVCS) on board the Solar and Heliospheric Observatory (SOHO) simultaneously in the hydrogen Lα and C III lines. We develop the non-LTE (departures from the local thermodynamic equilibrium - LTE) spectral diagnostics based on Lα and Lβ measured integrated intensities to derive other physical quantities of the hot erupting prominence. Based on this, we synthesize the C III line intensity to compare it with observations. Methods: Our method is based on non-LTE modeling of eruptive prominences. We used a general non-LTE radiative-transfer code only for optically thin prominence points because optically thick points do not allow the direct determination of the kinetic temperature and microturbulence from the line profiles. The input parameters of the code were the kinetic temperature and microturbulent velocity derived from the Lα and C III line widths, as well as the integrated intensity of the Lα and Lβ lines. The code runs in three loops to compute the radial flow velocity, electron density, and effective thickness as the best fit to the Lα and Lβ integrated intensities within the accuracy defined by the absolute radiometric calibration of UVCS data. Results: We analyzed 39 observational points along the whole erupting prominence because for these points we found a solution for the kinetic temperature and microturbulent velocity. For these points we ran the non-LTE code to determine best-fit models. All models with τ0(Lα) ≤ 0.3 and τ0(C III) ≤ 0.3 were analyzed further, for which we computed the integrated intensity of the C III line using a two-level atom. The best agreement between computed and observed integrated intensity led to 30 optically thin points along the prominence. The results are presented as histograms of the kinetic temperature, microturbulent velocity, effective thickness, radial flow velocity, electron density, and gas pressure. We also show the relation between the microturbulence and kinetic temperature together with a scatter plot of computed versus observed C III integrated intensities and the ratio of the computed to observed C III integrated intensities versus kinetic temperature. Conclusions: The erupting prominence embedded in the CME is relatively hot with a low electron density, a wide range of effective thicknesses, a rather narrow range of radial flow velocities, and a microturbulence of about 25 km s-1. This analysis shows a disagreement between observed and synthetic intensities of the C III line, the reason for which most probably is that photoionization is neglected in calculations of the ionization equilibrium. Alternatively, the disagreement might be due to non-equilibrium processes.

Experimental strategies in carrying out VCU for tobacco crop I: plot design and size.

PubMed

Toledo, F H R B; Ramalho, M A P; Pulcinelli, C E; Bruzi, A T

2013-09-19

We aimed to establish standards for tobacco Valor de Cultivo e Uso (VCU) in Brazil. We obtained information regarding the size and design of plots of two varietal groups of tobacco (Virginia and Burley). Ten inbred lines of each varietal group were evaluated in a randomized complete block design with four replications. The plot contained 42 plants with six rows of seven columns each. For each experiment plant, considering the position of the respective plant in the plot (row and column) as a reference, cured leaf weight (g/plant), total sugar content (%), and total alkaloid content (%) were determined. The maximum curvature of the variations in coefficients was estimated. Trials with the number of plants per plot ranging from 2 to 41 were simulated. The use of a border was not justified because the interactions between inbred lines x position in the plots were never significant, showing that the behavior of the inbred lines coincided with the different positions. The plant performance varied according to the column position in the plot. To lessen the effect of this factor, the use of plots with more than one row is recommended. Experimental precision, evaluated by the CV%, increased with an increase in plot size; nevertheless, the maximum curvature of the variation coefficient method showed no expressive increase in precision if the number of plants was greater than seven. The result in identification of the best inbred line, in terms of the size of each plot, coincided with the maximum curvature method.

Visual analytics of large multidimensional data using variable binned scatter plots

NASA Astrophysics Data System (ADS)

Hao, Ming C.; Dayal, Umeshwar; Sharma, Ratnesh K.; Keim, Daniel A.; Janetzko, Halldór

2010-01-01

The scatter plot is a well-known method of visualizing pairs of two-dimensional continuous variables. Multidimensional data can be depicted in a scatter plot matrix. They are intuitive and easy-to-use, but often have a high degree of overlap which may occlude a significant portion of data. In this paper, we propose variable binned scatter plots to allow the visualization of large amounts of data without overlapping. The basic idea is to use a non-uniform (variable) binning of the x and y dimensions and plots all the data points that fall within each bin into corresponding squares. Further, we map a third attribute to color for visualizing clusters. Analysts are able to interact with individual data points for record level information. We have applied these techniques to solve real-world problems on credit card fraud and data center energy consumption to visualize their data distribution and cause-effect among multiple attributes. A comparison of our methods with two recent well-known variants of scatter plots is included.

Development of Soil Characteristics and Plant Communities On Reclaimed and Unreclaimed Spoil Heaps After Coal Mining

NASA Astrophysics Data System (ADS)

Cudlín, Ondřej; Řehák, Zdeněk; Cudlín, Pavel

2016-10-01

The aim of this study was to compare soil characteristics, plant communities and the rate of selected ecosystem function performance on reclaimed and unreclaimed plots (left for spontaneous succession) of different age on spoil heaps. Twelve spoil heaps (three circle plots of radius 12.5 m) near the town Kladno in north-west direction from Prague, created after deep coal mining, were compared. Five mixed soil samples from organo-mineral horizons in each plot were analysed for total content of carbon, nitrogen and phosphorus. In addition, active soil pH (pHH2O) was determined. Plant diversity was determined by vegetation releves. The biodiversity value of the habitat according to the Habitat Valuation Method was assessed and the rate of evapotranspiration function by the Method of Valuation Functions and Services of Ecosystems in the Czech Republic were determined. The higher organo-mineral layers and higher amount of total nitrogen content were found on the older reclaimed and unreclaimed plots than in younger plots. The number of plant species and the total contents of carbon and nitrogen were significantly higher at the unreclaimed plots compared to reclaimed plots. The biodiversity values and evapotranspiration function rate were also higher on unreclaimed plots. From this perspective, it is possible to recommend using of spontaneous succession, together with routine reclamation methods to restore habitats after coal mining. Despite the relatively high age of vegetation in some of selected plots (90 years), both the reclaimed and unreclaimed plots have not reached the stage of potential vegetation near to natural climax. Slow development of vegetation was probably due to unsuitable substrate of spoil heaps and a lack of plant and tree species of natural forest habitats in this area. However, it is probable that vegetation communities on observed spoil heaps in both type of management (reclaimed and unreclaimed) will achieve the stage of natural climax and they will provide ecosystem functions more effectively in the future.

Fuzzy recurrence plots

NASA Astrophysics Data System (ADS)

Pham, T. D.

2016-12-01

Recurrence plots display binary texture of time series from dynamical systems with single dots and line structures. Using fuzzy recurrence plots, recurrences of the phase-space states can be visualized as grayscale texture, which is more informative for pattern analysis. The proposed method replaces the crucial similarity threshold required by symmetrical recurrence plots with the number of cluster centers, where the estimate of the latter parameter is less critical than the estimate of the former.

Analytical study on different blade-shape design of HAWT for wasted kinetic energy recovery system (WKERS)

NASA Astrophysics Data System (ADS)

Goh, J. B.; Jamaludin, Z.; Jafar, F. A.; Mat Ali, M.; Mokhtar, M. N. Ali; Tan, C. H.

2017-06-01

Wasted kinetic energy recovery system (WKERS) is a wind renewable gadget installed above a cooling tower outlet to harvest the discharged wind for electrical regeneration purpose. The previous WKERS is operated by a horizontal axis wind turbine (HAWT) with delta blade design but the performance is still not at the optimum level. Perhaps, a better blade-shape design should be determined to obtain the optimal performance, as it is believed that the blade-shape design plays a critical role in HAWT. Hence, to determine a better blade-shape design for a new generation of WKERS, elliptical blade, swept blade and NREL Phase IV blade are selected for this benchmarking process. NREL Phase IV blade is a modern HAWT’s blade design by National Renewable Energy Laboratory (NREL) research lab. During the process of benchmarking, Computational Fluid Dynamics (CFD) analysis was ran by using SolidWorks design software, where all the designs are simulated with linear flow simulation. The wind speed in the simulation is set at 10.0 m/s, which is compatible with the average wind speed produced by a standard size cooling tower. The result is obtained by flow trajectories of air motion, surface plot and cut plot of the applied blade-shape. Besides, the aspect ratio of each blade is calculated and included as one of the reference in the comparison. Hence, the final selection of the best blade-shape design will bring to the new generation of WKERS.

Studies of the kinetics and mechanism of the oxidation of uranium by dry and moist air A model for determining the oxidation rate over a wide range of temperatures and water vapour pressures

NASA Astrophysics Data System (ADS)

McGillivray, G. W.; Geeson, D. A.; Greenwood, R. C.

1994-01-01

The rate of oxidation of uranium metal by moist air has been measured at temperatures from 115 to 350°C and water vapour pressures from 0 to 47 kPa (350 Torr). From this and from previously reported data, a model has been developed which allows the rate of uranium oxidation to be calculated at any particular combination of temperature and water vapour pressure of interest, in the range 0-350°C and 0-101.3 kPa (760 Torr). The model is based on the assumption that the surface concentration of water determines the rate of reaction and that the adsorption of water onto the oxide follows a Langmuir type isotherm. Theoretical plots of rate as a function of water vapour pressure and Arrhenius plots derived from the model have been shown to be in good agreement with experimental data. The model assumes separate contributions to the overall observed rate from oxygen and water vapour. Surface studies have been carried out using SIMS (secondary ion mass spectrometry). Depth profiling of the oxide produced by isotopically labelled reagents ( 18O 2 and H 218O), has shown that oxygen from both reactants is incorporated into the oxide layer in the ratio predicted by the kinetic model. This supports a mechanism in which oxygen and water vapour produce separate diffusing species (possibly O 2- and OH -).

Synthesis, computational studies and enzyme inhibitory kinetics of substituted methyl[2-(4-dimethylamino-benzylidene)-hydrazono)-4-oxo-thiazolidin-5-ylidene]acetates as mushroom tyrosinase inhibitors.

PubMed

Channar, Pervaiz Ali; Saeed, Aamer; Larik, Fayaz Ali; Rafiq, Muhammad; Ashraf, Zaman; Jabeen, Farukh; Fattah, Tanzeela Abdul

2017-11-01

The present article describes the synthesis and enzyme inhibitory kinetics of methyl[2-(arylmethylene-hydrazono)-4-oxo-thiazolidin-5-ylidene]acetates 5a-j as mushroom tyrosinase inhibitors. The title compounds were synthesized via cyclocondensation of thiosemicarbazones 3a-j with dimethyl but-2-ynedioate (DMAD) 4 in good yields under solvent-free conditions. The synthesized compounds were evaluated for their potential to inhibit the activity of mushroom tyrosinase. It was unveiled that compounds 5i showed excellent enzyme inhibitory activity with IC 50 3.17µM while IC 50 of standard kojic acid is 15.91µM. The presence of heterocyclic pyridine ring in compound 5i play important role in enzyme inhibitory activity as rest of the functional groups are common in all synthesized compounds. The enzyme inhibitory kinetics of the most potent derivative 5i determined by Lineweaver-Burk plots and Dixon plots showed that it is non-competitive inhibitor with Ki value 1.5µM. It was further investigated that the wet lab results are in good agreement with the computational results. The molecular docking of the synthesized compounds was performed against tyrosinase protein (PDBID 2Y9X) to delineate ligand-protein interactions at molecular level. The docking results showed that the major interacting residues are His244, His85, His263, Val 283, His 296, Asn260, Val248, His260, His261 and Phe264 which are located in active binding site of the protein. The molecular modeling demonstrates that the oxygen atom of the compound 5i coordinated with the key residues in the active site of mushroom tyrosinase contribute significantly against inhibitory ability and diminishing the human melanin synthesis. These results evident that compound 5i is a lead structure in developing most potent mushroom tyrosinase inhibitors. Copyright © 2017 Elsevier Ltd. All rights reserved.

Trends in Selective Hydrogen Peroxide Production on Transition Metal Surfaces from First Principles

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

Rankin, Rees B.; Greeley, Jeffrey P.

2012-10-19

We present a comprehensive, Density Functional Theory-based analysis of the direct synthesis of hydrogen peroxide, H2O2, on twelve transition metal surfaces. We determine the full thermodynamics and selected kinetics of the reaction network on these metals, and we analyze these energetics with simple, microkinetically motivated rate theories to assess the activity and selectivity of hydrogen peroxide production on the surfaces of interest. By further exploiting Brønsted-Evans-Polanyi relationships and scaling relationships between the binding energies of different adsorbates, we express the results in the form of a two dimensional contour volcano plot, with the activity and selectivity being determined as functionsmore » of two independent descriptors, the atomic hydrogen and oxygen adsorption free energies. We identify both a region of maximum predicted catalytic activity, which is near Pt and Pd in descriptor space, and a region of selective hydrogen peroxide production, which includes Au. The optimal catalysts represent a compromise between activity and selectivity and are predicted to fall approximately between Au and Pd in descriptor space, providing a compact explanation for the experimentally known performance of Au-Pd alloys for hydrogen peroxide synthesis, and suggesting a target for future computational screening efforts to identify improved direct hydrogen peroxide synthesis catalysts. Related methods of combining activity and selectivity analysis into a single volcano plot may be applicable to, and useful for, other aqueous phase heterogeneous catalytic reactions where selectivity is a key catalytic criterion.« less

Highly sensitive catalytic spectrophotometric determination of ruthenium

NASA Astrophysics Data System (ADS)

Naik, Radhey M.; Srivastava, Abhishek; Prasad, Surendra

2008-01-01

A new and highly sensitive catalytic kinetic method (CKM) for the determination of ruthenium(III) has been established based on its catalytic effect on the oxidation of L-phenylalanine ( L-Pheala) by KMnO 4 in highly alkaline medium. The reaction has been followed spectrophotometrically by measuring the decrease in the absorbance at 526 nm. The proposed CKM is based on the fixed time procedure under optimum reaction conditions. It relies on the linear relationship where the change in the absorbance (Δ At) versus added Ru(III) amounts in the range of 0.101-2.526 ng ml -1 is plotted. Under the optimum conditions, the sensitivity of the proposed method, i.e. the limit of detection corresponding to 5 min is 0.08 ng ml -1, and decreases with increased time of analysis. The method is featured with good accuracy and reproducibility for ruthenium(III) determination. The ruthenium(III) has also been determined in presence of several interfering and non-interfering cations, anions and polyaminocarboxylates. No foreign ions interfered in the determination ruthenium(III) up to 20-fold higher concentration of foreign ions. In addition to standard solutions analysis, this method was successfully applied for the quantitative determination of ruthenium(III) in drinking water samples. The method is highly sensitive, selective and very stable. A review of recently published catalytic spectrophotometric methods for the determination of ruthenium(III) has also been presented for comparison.

Three-dimensional reconstruction of single-cell chromosome structure using recurrence plots.

PubMed

Hirata, Yoshito; Oda, Arisa; Ohta, Kunihiro; Aihara, Kazuyuki

2016-10-11

Single-cell analysis of the three-dimensional (3D) chromosome structure can reveal cell-to-cell variability in genome activities. Here, we propose to apply recurrence plots, a mathematical method of nonlinear time series analysis, to reconstruct the 3D chromosome structure of a single cell based on information of chromosomal contacts from genome-wide chromosome conformation capture (Hi-C) data. This recurrence plot-based reconstruction (RPR) method enables rapid reconstruction of a unique structure in single cells, even from incomplete Hi-C information.

Three-dimensional reconstruction of single-cell chromosome structure using recurrence plots

NASA Astrophysics Data System (ADS)

Hirata, Yoshito; Oda, Arisa; Ohta, Kunihiro; Aihara, Kazuyuki

2016-10-01

Single-cell analysis of the three-dimensional (3D) chromosome structure can reveal cell-to-cell variability in genome activities. Here, we propose to apply recurrence plots, a mathematical method of nonlinear time series analysis, to reconstruct the 3D chromosome structure of a single cell based on information of chromosomal contacts from genome-wide chromosome conformation capture (Hi-C) data. This recurrence plot-based reconstruction (RPR) method enables rapid reconstruction of a unique structure in single cells, even from incomplete Hi-C information.

Use of recurrence plots in the analysis of pupil diameter dynamics in narcoleptics

NASA Astrophysics Data System (ADS)

Keegan, Andrew P.; Zbilut, J. P.; Merritt, S. L.; Mercer, P. J.

1993-11-01

Recurrence plots were used to evaluate pupil dynamics of subjects with narcolepsy. Preliminary data indicate that this nonlinear method of analyses may be more useful in revealing underlying deterministic differences than traditional methods like FFT and counting statistics.

Second-order kinetic model for the sorption of cadmium onto tree fern: a comparison of linear and non-linear methods.

PubMed

Ho, Yuh-Shan

2006-01-01

A comparison was made of the linear least-squares method and a trial-and-error non-linear method of the widely used pseudo-second-order kinetic model for the sorption of cadmium onto ground-up tree fern. Four pseudo-second-order kinetic linear equations are discussed. Kinetic parameters obtained from the four kinetic linear equations using the linear method differed but they were the same when using the non-linear method. A type 1 pseudo-second-order linear kinetic model has the highest coefficient of determination. Results show that the non-linear method may be a better way to obtain the desired parameters.

Multi-Reader ROC studies with Split-Plot Designs: A Comparison of Statistical Methods

PubMed Central

Obuchowski, Nancy A.; Gallas, Brandon D.; Hillis, Stephen L.

2012-01-01

Rationale and Objectives Multi-reader imaging trials often use a factorial design, where study patients undergo testing with all imaging modalities and readers interpret the results of all tests for all patients. A drawback of the design is the large number of interpretations required of each reader. Split-plot designs have been proposed as an alternative, in which one or a subset of readers interprets all images of a sample of patients, while other readers interpret the images of other samples of patients. In this paper we compare three methods of analysis for the split-plot design. Materials and Methods Three statistical methods are presented: Obuchowski-Rockette method modified for the split-plot design, a newly proposed marginal-mean ANOVA approach, and an extension of the three-sample U-statistic method. A simulation study using the Roe-Metz model was performed to compare the type I error rate, power and confidence interval coverage of the three test statistics. Results The type I error rates for all three methods are close to the nominal level but tend to be slightly conservative. The statistical power is nearly identical for the three methods. The coverage of 95% CIs fall close to the nominal coverage for small and large sample sizes. Conclusions The split-plot MRMC study design can be statistically efficient compared with the factorial design, reducing the number of interpretations required per reader. Three methods of analysis, shown to have nominal type I error rate, similar power, and nominal CI coverage, are available for this study design. PMID:23122570

Co-pyrolysis behaviour and kinetic of two typical solid wastes in China and characterisation of activated carbon prepared from pyrolytic char.

PubMed

Ma, Yuhui; Niu, Ruxuan; Wang, Xiaona; Wang, Qunhui; Wang, Xiaoqiang; Sun, Xiaohong

2014-11-01

This is the first study on the co-pyrolysis of spent substrate of Pleurotus ostreatus and coal tar pitch, and the activated carbon prepared from the pyrolytic char. Thermogravimetry (TG) analysis was carried out taking spent substrate, coal tar pitch and spent substrate-coal tar pitch mixture. The activation energies of pyrolysis reactions were obtained via the Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose methods. The kinetic models were determined by the master-plots method. The activated carbons were characterised by N2-adsorption, Fourier transform infrared spectroscopy and X-ray diffraction. Experimental results demonstrated a synergistic effect happened during co-pyrolysis, which was characterised by a decreased maximum decomposition rate and an enhanced char yield. The average activation energies of the pyrolysis reactions of spent substrate, coal tar pitch and the mixture were 115.94, 72.92 and 94.38 kJ mol(-1) for the Flynn-Wall-Ozawa method, and 112.17, 65.62 and 89.91 kJ mol(-1) for the Kissinger-Akahira-Sunose method. The reaction model functions were f(α) = (1-α)(3.42), (1-α)(1.72) and (1-α)(3.07) for spent substrate, coal tar pitch and the mixture, respectively. The mixture char-derived activated carbon had a Brunauer-Emmett-Teller surface area up to 1337 m(2) g(-1) and a total pore volume of 0.680 cm(3) g(-1). Mixing spent substrate with coal tar pitch led to the creation of more micropores and a higher surface area compared with the single spent substrate and coal tar pitch char. Also, the mixture char-derived activated carbon had a higher proportion of aromatic stacking. This study provides a reference for the utilisation of spent substrate and coal tar pitch via co-pyrolysis, and their pyrolytic char as a promising precursor of activated carbon. © The Author(s) 2014.

Confidence limits for contribution plots in multivariate statistical process control using bootstrap estimates.

PubMed

Babamoradi, Hamid; van den Berg, Frans; Rinnan, Åsmund

2016-02-18

In Multivariate Statistical Process Control, when a fault is expected or detected in the process, contribution plots are essential for operators and optimization engineers in identifying those process variables that were affected by or might be the cause of the fault. The traditional way of interpreting a contribution plot is to examine the largest contributing process variables as the most probable faulty ones. This might result in false readings purely due to the differences in natural variation, measurement uncertainties, etc. It is more reasonable to compare variable contributions for new process runs with historical results achieved under Normal Operating Conditions, where confidence limits for contribution plots estimated from training data are used to judge new production runs. Asymptotic methods cannot provide confidence limits for contribution plots, leaving re-sampling methods as the only option. We suggest bootstrap re-sampling to build confidence limits for all contribution plots in online PCA-based MSPC. The new strategy to estimate CLs is compared to the previously reported CLs for contribution plots. An industrial batch process dataset was used to illustrate the concepts. Copyright © 2016 Elsevier B.V. All rights reserved.

A Century of Enzyme Kinetic Analysis, 1913 to 2013

PubMed Central

Johnson, Kenneth A.

2013-01-01

This review traces the history and logical progression of methods for quantitative analysis of enzyme kinetics from the 1913 Michaelis and Menten paper to the application of modern computational methods today. Following a brief review of methods for fitting steady state kinetic data, modern methods are highlighted for fitting full progress curve kinetics based upon numerical integration of rate equations, including a re-analysis of the original Michaelis-Menten full time course kinetic data. Finally, several illustrations of modern transient state kinetic methods of analysis are shown which enable the elucidation of reactions occurring at the active sites of enzymes in order to relate structure and function. PMID:23850893

Evaluation of a reproductive index to estimate grasshopper sparrow and eastern meadowlark reproductive success

USGS Publications Warehouse

Althoff, Donald P.; Gipson, P.S.; Pontius, J.S.; Japuntich, R.D.

2009-01-01

We compared an index of reproductive success based on breeding behavior to actual nest fates of grasshopper sparrows (Ammodramus savannarum) and eastern meadowlarks (Sturnella magna) on 12 plots (4-ha). Concordance of results between the two methods was 58% for grasshopper sparrows and 42% for eastern meadowlarks on a plot-by-plot basis. The indirect method yielded higher estimates of reproductive activity than nest monitoring for the balance of the plots,. There was little evidence that brown-headed cowbird (Molothrus ater) parasitism influenced the estimates of reproductive success using the indirect method. We concluded that nests and about-to-fledge nestlings were missed during searches on some plots. It may be appropriate to use an indirect method to more efficiently survey territories and/or plots for species with hard-to-find nests or when monitoring large areas. Use of a reproductive index may be appropriate and more time-efficient than nest searching and monitoring for comparing management effects such as burning, grazing, haying, military training, and other localized disturbances that are likely to affect reproductive success of grasshopper sparrows and eastern meadowlarks. However, nest monitoring may be necessary for more precise estimates of productivity necessary for long-term monitoring. Nest monitoring results are also likely to allow for direct comparisons to results from other studies because the index method requires intimate knowledge of the species being evaluated - a factor that could lead to reduced precision because the experience level of technicians relying only on behavioral cues from study-to-study is likely to vary considerably.

Funnel plot control limits to identify poorly performing healthcare providers when there is uncertainty in the value of the benchmark.

PubMed

Manktelow, Bradley N; Seaton, Sarah E; Evans, T Alun

2016-12-01

There is an increasing use of statistical methods, such as funnel plots, to identify poorly performing healthcare providers. Funnel plots comprise the construction of control limits around a benchmark and providers with outcomes falling outside the limits are investigated as potential outliers. The benchmark is usually estimated from observed data but uncertainty in this estimate is usually ignored when constructing control limits. In this paper, the use of funnel plots in the presence of uncertainty in the value of the benchmark is reviewed for outcomes from a Binomial distribution. Two methods to derive the control limits are shown: (i) prediction intervals; (ii) tolerance intervals Tolerance intervals formally include the uncertainty in the value of the benchmark while prediction intervals do not. The probability properties of 95% control limits derived using each method were investigated through hypothesised scenarios. Neither prediction intervals nor tolerance intervals produce funnel plot control limits that satisfy the nominal probability characteristics when there is uncertainty in the value of the benchmark. This is not necessarily to say that funnel plots have no role to play in healthcare, but that without the development of intervals satisfying the nominal probability characteristics they must be interpreted with care. © The Author(s) 2014.

MID Plot: a new lithology technique. [Matrix identification plot

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

Clavier, C.; Rust, D.H.

1976-01-01

Lithology interpretation by the Litho-Porosity (M-N) method has been used for years, but is evidently too cumbersome and ambiguous for widespread acceptance as a field technique. To set aside these objections, another method has been devised. Instead of the log-derived parameters M and N, the MID Plot uses quasi-physical quantities, (rho/sub ma/)/sub a/ and (..delta..t/sub ma/)/sub a/, as its porosity-independent variables. These parameters, taken from suitably scaled Neutron-Density and Sonic-Neutron crossplots, define a unique matrix mineral or mixture for each point on the logs. The matrix points on the MID Plot thus remain constant in spite of changes in mudmore » filtrate, porosity, or neutron tool types (all of which significantly affect the M-N Plot). This new development is expected to bring welcome relief in areas where lithology identification is a routine part of log analysis.« less

Linear and non-linear regression analysis for the sorption kinetics of methylene blue onto activated carbon.

PubMed

Kumar, K Vasanth

2006-10-11

Batch kinetic experiments were carried out for the sorption of methylene blue onto activated carbon. The experimental kinetics were fitted to the pseudo first-order and pseudo second-order kinetics by linear and a non-linear method. The five different types of Ho pseudo second-order expression have been discussed. A comparison of linear least-squares method and a trial and error non-linear method of estimating the pseudo second-order rate kinetic parameters were examined. The sorption process was found to follow a both pseudo first-order kinetic and pseudo second-order kinetic model. Present investigation showed that it is inappropriate to use a type 1 and type pseudo second-order expressions as proposed by Ho and Blanachard et al. respectively for predicting the kinetic rate constants and the initial sorption rate for the studied system. Three correct possible alternate linear expressions (type 2 to type 4) to better predict the initial sorption rate and kinetic rate constants for the studied system (methylene blue/activated carbon) was proposed. Linear method was found to check only the hypothesis instead of verifying the kinetic model. Non-linear regression method was found to be the more appropriate method to determine the rate kinetic parameters.

Kinetic buffers.

PubMed

Alibrandi, Giuseppe; Fabbrizzi, Luigi; Licchelli, Maurizio; Puglisi, Antonio

2015-01-12

This paper proposes a new type of molecular device that is able to act as an inverse proton sponge to slowly decrease the pH inside a reaction vessel. This makes the automatic monitoring of the concentration of pH-sensitive systems possible. The device is a composite formed of an alkyl chloride, which kinetically produces acidity, and a buffer that thermodynamically modulates the variation in pH value. Profiles of pH versus time (pH-t plots) have been generated under various experimental conditions by computer simulation, and the device has been tested by carrying out automatic spectrophotometric titrations, without using an autoburette. To underline the wide variety of possible applications, this new system has been used to realize and monitor HCl uptake by a di-copper(II) bistren complex in a single run, in a completely automatic experiment. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetic theory of oxygen isotopic exchange between minerals and water

USGS Publications Warehouse

Criss, R.E.; Gregory, R.T.; Taylor, H.P.

1987-01-01

Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in "closed" and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation of mass equation. The simultaneous solutions to these equations generate curved exchange trajectories on ??-?? plots. Families of such trajectories generated under conditions allowing for different fluid mole fractions, different fluid isotopic compositions, or different fluid flow rates are connected by positive-sloped isochronous lines. These isochrons reproduce the effects observed in hydrothermally exchanged mineral pairs including 1) steep positive slopes, 2) common reversals in the measured fractionation factors (??), and 3) measured fractionations that are highly variable over short distances where no thermal gradient can be geologically demonstrated. ?? 1987.

Impact of surface wettability on S-layer recrystallization: a real-time characterization by QCM-D.

PubMed

Iturri, Jagoba; Vianna, Ana C; Moreno-Cencerrado, Alberto; Pum, Dietmar; Sleytr, Uwe B; Toca-Herrera, José Luis

2017-01-01

Quartz crystal microbalance with dissipation monitoring (QCM-D) has been employed to study the assembly and recrystallization kinetics of isolated SbpA bacterial surface proteins onto silicon dioxide substrates of different surface wettability. Surface modification by UV/ozone oxidation or by vapor deposition of 1 H ,1 H ,2 H ,2 H -perfluorododecyltrichlorosilane yielded hydrophilic or hydrophobic samples, respectively. Time evolution of frequency and dissipation factors, either individually or combined as the so-called Df plots, showed a much faster formation of crystalline coatings for hydrophobic samples, characterized by a phase-transition peak at around the 70% of the total mass adsorbed. This behavior has been proven to mimic, both in terms of kinetics and film assembly steps, the recrystallization taking place on an underlying secondary cell-wall polymer (SCWP) as found in bacteria. Complementary atomic force microscopy (AFM) experiments corroborate these findings and reveal the impact on the final structure achieved.

SnagPRO: snag and tree sampling and analysis methods for wildlife

Treesearch

Lisa J. Bate; Michael J. Wisdom; Edward O. Garton; Shawn C. Clabough

2008-01-01

We describe sampling methods and provide software to accurately and efficiently estimate snag and tree densities at desired scales to meet a variety of research and management objectives. The methods optimize sampling effort by choosing a plot size appropriate for the specified forest conditions and sampling goals. Plot selection and data analyses are supported by...

Weighted analysis methods for mapped plot forest inventory data: Tables, regressions, maps and graphs

Treesearch

Paul C. Van Deusen; Linda S. Heath

2010-01-01

Weighted estimation methods for analysis of mapped plot forest inventory data are discussed. The appropriate weighting scheme can vary depending on the type of analysis and graphical display. Both statistical issues and user expectations need to be considered in these methods. A weighting scheme is proposed that balances statistical considerations and the logical...

Modeling the uncertainty of estimating forest carbon stocks in China

NASA Astrophysics Data System (ADS)

Yue, T. X.; Wang, Y. F.; Du, Z. P.; Zhao, M. W.; Zhang, L. L.; Zhao, N.; Lu, M.; Larocque, G. R.; Wilson, J. P.

2015-12-01

Earth surface systems are controlled by a combination of global and local factors, which cannot be understood without accounting for both the local and global components. The system dynamics cannot be recovered from the global or local controls alone. Ground forest inventory is able to accurately estimate forest carbon stocks at sample plots, but these sample plots are too sparse to support the spatial simulation of carbon stocks with required accuracy. Satellite observation is an important source of global information for the simulation of carbon stocks. Satellite remote-sensing can supply spatially continuous information about the surface of forest carbon stocks, which is impossible from ground-based investigations, but their description has considerable uncertainty. In this paper, we validated the Lund-Potsdam-Jena dynamic global vegetation model (LPJ), the Kriging method for spatial interpolation of ground sample plots and a satellite-observation-based approach as well as an approach for fusing the ground sample plots with satellite observations and an assimilation method for incorporating the ground sample plots into LPJ. The validation results indicated that both the data fusion and data assimilation approaches reduced the uncertainty of estimating carbon stocks. The data fusion had the lowest uncertainty by using an existing method for high accuracy surface modeling to fuse the ground sample plots with the satellite observations (HASM-SOA). The estimates produced with HASM-SOA were 26.1 and 28.4 % more accurate than the satellite-based approach and spatial interpolation of the sample plots, respectively. Forest carbon stocks of 7.08 Pg were estimated for China during the period from 2004 to 2008, an increase of 2.24 Pg from 1984 to 2008, using the preferred HASM-SOA method.

Problems with sampling desert tortoises: A simulation analysis based on field data

USGS Publications Warehouse

Freilich, J.E.; Camp, R.J.; Duda, J.J.; Karl, A.E.

2005-01-01

The desert tortoise (Gopherus agassizii) was listed as a U.S. threatened species in 1990 based largely on population declines inferred from mark-recapture surveys of 2.59-km2 (1-mi2) plots. Since then, several census methods have been proposed and tested, but all methods still pose logistical or statistical difficulties. We conducted computer simulations using actual tortoise location data from 2 1-mi2 plot surveys in southern California, USA, to identify strengths and weaknesses of current sampling strategies. We considered tortoise population estimates based on these plots as "truth" and then tested various sampling methods based on sampling smaller plots or transect lines passing through the mile squares. Data were analyzed using Schnabel's mark-recapture estimate and program CAPTURE. Experimental subsampling with replacement of the 1-mi2 data using 1-km2 and 0.25-km2 plot boundaries produced data sets of smaller plot sizes, which we compared to estimates from the 1-mi 2 plots. We also tested distance sampling by saturating a 1-mi 2 site with computer simulated transect lines, once again evaluating bias in density estimates. Subsampling estimates from 1-km2 plots did not differ significantly from the estimates derived at 1-mi2. The 0.25-km2 subsamples significantly overestimated population sizes, chiefly because too few recaptures were made. Distance sampling simulations were biased 80% of the time and had high coefficient of variation to density ratios. Furthermore, a prospective power analysis suggested limited ability to detect population declines as high as 50%. We concluded that poor performance and bias of both sampling procedures was driven by insufficient sample size, suggesting that all efforts must be directed to increasing numbers found in order to produce reliable results. Our results suggest that present methods may not be capable of accurately estimating desert tortoise populations.

Progesterone binding nano-carriers based on hydrophobically modified hyperbranched polyglycerols

NASA Astrophysics Data System (ADS)

Alizadeh Noghani, M.; Brooks, D. E.

2016-02-01

Progesterone (Pro) is a potent neurosteroid and promotes recovery from moderate Traumatic Brain Injury but its clinical application is severely impeded by its poor water solubility. Here we demonstrate that reversibly binding Pro within hydrophobically modified hyperbranched polyglycerol (HPG-Cn-MPEG) enhances its solubility, stability and bioavailability. Synthesis, characterization and Pro loading into HPG-Cn-MPEG is described. The release kinetics are correlated with structural properties and the results of Differential Scanning Calorimetry studies of a family of HPG-Cn-MPEGs of varying molecular weight and alkylation. While the maximum amount of Pro bound correlates well with the amount of alkyl carbon per molecule contributing to its hydrophobicity, the dominant first order rate constant for Pro release correlates strongly with the amount of structured or bound water in the dendritic domain of the polymer. The results provide evidence to justify more detailed studies of interactions with biological systems, both single cells and in animal models.Progesterone (Pro) is a potent neurosteroid and promotes recovery from moderate Traumatic Brain Injury but its clinical application is severely impeded by its poor water solubility. Here we demonstrate that reversibly binding Pro within hydrophobically modified hyperbranched polyglycerol (HPG-Cn-MPEG) enhances its solubility, stability and bioavailability. Synthesis, characterization and Pro loading into HPG-Cn-MPEG is described. The release kinetics are correlated with structural properties and the results of Differential Scanning Calorimetry studies of a family of HPG-Cn-MPEGs of varying molecular weight and alkylation. While the maximum amount of Pro bound correlates well with the amount of alkyl carbon per molecule contributing to its hydrophobicity, the dominant first order rate constant for Pro release correlates strongly with the amount of structured or bound water in the dendritic domain of the polymer. The results provide evidence to justify more detailed studies of interactions with biological systems, both single cells and in animal models. Electronic supplementary information (ESI) available: Fig. S-1: chemical structure of progesterone (Pro). Fig. S-2: 1H NMR spectrum of HPG-C8-MPEG. Fig. S-3: GPC chromatogram of HPG-C8-MPEG. Fig. S-4: 1H NMR spectrum of HPG-C12-MPEG. Fig. S-5: GPC chromatogram of HPG-C8-MPEG. Fig. S-6: FTIR spectrum of HPG-C8-MPEG. Fig. S-7: inverse-gated 13C NMR spectrum of HPG-C8-MPEG in methanol-d4. Fig. S-8: semi-log plot to determine initial rapid release kinetics for HPG-C8-MPEG/Pro in PBS. Fig. S-9: semi-log plot to determine secondary slow release kinetics for HPG-C8-MPEG/Pro in PBS. Fig. S-10: semi-log plot illustrating the kinetics of Pro release from HPG-C8-MPEG/Pro in plasma. Fig. S-11: dependence of k1 and Vp - Va. Fig. S-12: correlation between the maximum binding capacity of HPG-Cn-MPEG polymeric systems for binding Pro and their total mass of alkyl carbon external to the oxygen (R2 = 0.77 and p < 0.025). Table S-1: effect of loaded Pro on HPG-Cn-MPEG size. Fig. S-13. DLS size determination of HPG-C10-MPEG at 2 mg ml-1 (on the left) and HPG-C10-MPEG/Pro at 2 mg ml-1 of polymer and 25 μg ml-1 of Pro (on the right). The minor population of larger particles was reduced in diameter by Pro binding, illustrated above, consistent with an earlier report.11 See DOI: 10.1039/c5nr08175k

Graphic report of the results from propensity score method analyses.

PubMed

Shrier, Ian; Pang, Menglan; Platt, Robert W

2017-08-01

To increase transparency in studies reporting propensity scores by using graphical methods that clearly illustrate (1) the number of participant exclusions that occur as a consequence of the analytic strategy and (2) whether treatment effects are constant or heterogeneous across propensity scores. We applied graphical methods to a real-world pharmacoepidemiologic study that evaluated the effect of initiating statin medication on the 1-year all-cause mortality post-myocardial infarction. We propose graphical methods to show the consequences of trimming and matching on the exclusion of participants from the analysis. We also propose the use of meta-analytical forest plots to show the magnitude of effect heterogeneity. A density plot with vertical lines demonstrated the proportion of subjects excluded because of trimming. A frequency plot with horizontal lines demonstrated the proportion of subjects excluded because of matching. An augmented forest plot illustrates the amount of effect heterogeneity present in the data. Our proposed techniques present additional and useful information that helps readers understand the sample that is analyzed with propensity score methods and whether effect heterogeneity is present. Copyright © 2017 Elsevier Inc. All rights reserved.

Multi-reader ROC studies with split-plot designs: a comparison of statistical methods.

PubMed

Obuchowski, Nancy A; Gallas, Brandon D; Hillis, Stephen L

2012-12-01

Multireader imaging trials often use a factorial design, in which study patients undergo testing with all imaging modalities and readers interpret the results of all tests for all patients. A drawback of this design is the large number of interpretations required of each reader. Split-plot designs have been proposed as an alternative, in which one or a subset of readers interprets all images of a sample of patients, while other readers interpret the images of other samples of patients. In this paper, the authors compare three methods of analysis for the split-plot design. Three statistical methods are presented: the Obuchowski-Rockette method modified for the split-plot design, a newly proposed marginal-mean analysis-of-variance approach, and an extension of the three-sample U-statistic method. A simulation study using the Roe-Metz model was performed to compare the type I error rate, power, and confidence interval coverage of the three test statistics. The type I error rates for all three methods are close to the nominal level but tend to be slightly conservative. The statistical power is nearly identical for the three methods. The coverage of 95% confidence intervals falls close to the nominal coverage for small and large sample sizes. The split-plot multireader, multicase study design can be statistically efficient compared to the factorial design, reducing the number of interpretations required per reader. Three methods of analysis, shown to have nominal type I error rates, similar power, and nominal confidence interval coverage, are available for this study design. Copyright © 2012 AUR. All rights reserved.

Using recurrence plot analysis for software execution interpretation and fault detection

NASA Astrophysics Data System (ADS)

Mosdorf, M.

2015-09-01

This paper shows a method targeted at software execution interpretation and fault detection using recurrence plot analysis. In in the proposed approach recurrence plot analysis is applied to software execution trace that contains executed assembly instructions. Results of this analysis are subject to further processing with PCA (Principal Component Analysis) method that simplifies number coefficients used for software execution classification. This method was used for the analysis of five algorithms: Bubble Sort, Quick Sort, Median Filter, FIR, SHA-1. Results show that some of the collected traces could be easily assigned to particular algorithms (logs from Bubble Sort and FIR algorithms) while others are more difficult to distinguish.

Metadata (MD)

Treesearch

Robert E. Keane

2006-01-01

The Metadata (MD) table in the FIREMON database is used to record any information about the sampling strategy or data collected using the FIREMON sampling procedures. The MD method records metadata pertaining to a group of FIREMON plots, such as all plots in a specific FIREMON project. FIREMON plots are linked to metadata using a unique metadata identifier that is...

A method for subsurface-banding poultry litter in plots not accessible with conventional field equipment

USDA-ARS?s Scientific Manuscript database

Subsurface band application of poultry litter has been shown to be effective in reducing nutrients in runoff and leachate, relative to surface broadcast application of litter. Some field plot arrangements, such as plots having adjacent pits in the soil, prevent the use of conventional field equipme...

Smoothed Residual Plots for Generalized Linear Models. Technical Report #450.

ERIC Educational Resources Information Center

Brant, Rollin

Methods for examining the viability of assumptions underlying generalized linear models are considered. By appealing to the likelihood, a natural generalization of the raw residual plot for normal theory models is derived and is applied to investigating potential misspecification of the linear predictor. A smooth version of the plot is also…

Refining FIA plot locations using LiDAR point clouds

Treesearch

Charlie Schrader-Patton; Greg C. Liknes; Demetrios Gatziolis; Brian M. Wing; Mark D. Nelson; Patrick D. Miles; Josh Bixby; Daniel G. Wendt; Dennis Kepler; Abbey Schaaf

2015-01-01

Forest Inventory and Analysis (FIA) plot location coordinate precision is often insufficient for use with high resolution remotely sensed data, thereby limiting the use of these plots for geospatial applications and reducing the validity of models that assume the locations are precise. A practical and efficient method is needed to improve coordinate precision. To...

National FIA plot intensification procedure report

Treesearch

Jock A. Blackard; Paul L. Patterson

2014-01-01

The Forest Inventory and Analysis (FIA) program of the U.S. Forest Service (USFS) measures a spatially distributed base grid of forest inventory plots across the United States. The sampling intensity of plots may be increased in some regions when warranted by specific inventory objectives. Several intensification methods have been developed within FIA and USFS National...

Mapped Plot Patch Size Estimates

Treesearch

Paul C. Van Deusen

2005-01-01

This paper demonstrates that the mapped plot design is relatively easy to analyze and describes existing formulas for mean and variance estimators. New methods are developed for using mapped plots to estimate average patch size of condition classes. The patch size estimators require assumptions about the shape of the condition class, limiting their utility. They may...

Research on tactical information display technology for interactive virtual cockpit

NASA Astrophysics Data System (ADS)

Sun, Zhongyun; Tian, Tao; Su, Feng

2018-04-01

Based on a fact that traditional tactical information display technology suffers from disadvantages of a large number of data to be transferred and low plotting efficiency in an interactive virtual cockpit, a GID protocol-based simulation has been designed. This method dissolves complex tactical information screens into basic plotting units. The indication of plotting units is controlled via the plotting commands, which solves the incompatibility between the tactical information display in traditional simulation and the desktop-based virtual simulation training system. Having been used in desktop systems for helicopters, fighters, and transporters, this method proves to be scientific and reasonable in design and simple and efficient in usage, which exerts a significant value in establishing aviation equipment technology support training products.

Performance of quantitative vegetation sampling methods across gradients of cover in Great Basin plant communities

USGS Publications Warehouse

Pilliod, David S.; Arkle, Robert S.

2013-01-01

Resource managers and scientists need efficient, reliable methods for quantifying vegetation to conduct basic research, evaluate land management actions, and monitor trends in habitat conditions. We examined three methods for quantifying vegetation in 1-ha plots among different plant communities in the northern Great Basin: photography-based grid-point intercept (GPI), line-point intercept (LPI), and point-quarter (PQ). We also evaluated each method for within-plot subsampling adequacy and effort requirements relative to information gain. We found that, for most functional groups, percent cover measurements collected with the use of LPI, GPI, and PQ methods were strongly correlated. These correlations were even stronger when we used data from the upper canopy only (i.e., top “hit” of pin flags) in LPI to estimate cover. PQ was best at quantifying cover of sparse plants such as shrubs in early successional habitats. As cover of a given functional group decreased within plots, the variance of the cover estimate increased substantially, which required more subsamples per plot (i.e., transect lines, quadrats) to achieve reliable precision. For GPI, we found that that six–nine quadrats per hectare were sufficient to characterize the vegetation in most of the plant communities sampled. All three methods reasonably characterized the vegetation in our plots, and each has advantages depending on characteristics of the vegetation, such as cover or heterogeneity, study goals, precision of measurements required, and efficiency needed.

The Application of TD/GC/NICI-MS with an Al2O3-PLOT-S Column for the Determination of Perfluoroalkylcycloalkanes in the Atmosphere.

PubMed

Ren, Yu; Schlager, Hans; Martin, Damien

2014-01-01

A modified method for the quantitative determination of atmospheric perfluoroalkylcycloalkanes (PFCs) using thermal desorption coupled with gas chromatography and detection by negative ion chemical ionization-mass spectrometry was developed. Using an optimized analytical system, a commercially available Al 2 O 3 porous layer open tubular (PLOT) capillary column (30 m × 0.25 mm) deactivated with Na 2 SO 4 was used for separation of PFCs. Improvements in the separation of PFCs, the corresponding identification and the limit of detection of PFCs using this method and column are presented. The method was successfully applied to determine the atmospheric background concentrations of a range of PFCs from a number of samples collected at a rural site in Germany. The results of this study suggest that the method outlined using the Al 2 O 3 -PLOT-S capillary column has good sensitivity and selectivity, and that it can be deployed in a routine laboratory process for the analysis of PFCs in the future research work. In addition, the ability of this column to separate the isomers of one of the lower boiling PFCs (perfluorodimethylcyclobutane) and its ability to resolve perfluoroethylcyclohexane offer the opportunity for single-column analysis for multiple PFCs.

Harvesting tree biomass at the stand level to assess the accuracy of field and airborne biomass estimation in savannas.

PubMed

Colgan, Matthew S; Asner, Gregory P; Swemmer, Tony

2013-07-01

Tree biomass is an integrated measure of net growth and is critical for understanding, monitoring, and modeling ecosystem functions. Despite the importance of accurately measuring tree biomass, several fundamental barriers preclude direct measurement at large spatial scales, including the facts that trees must be felled to be weighed and that even modestly sized trees are challenging to maneuver once felled. Allometric methods allow for estimation of tree mass using structural characteristics, such as trunk diameter. Savanna trees present additional challenges, including limited available allometry and a prevalence of multiple stems per individual. Here we collected airborne lidar data over a semiarid savanna adjacent to the Kruger National Park, South Africa, and then harvested and weighed woody plant biomass at the plot scale to provide a standard against which field and airborne estimation methods could be compared. For an existing airborne lidar method, we found that half of the total error was due to averaging canopy height at the plot scale. This error was eliminated by instead measuring maximum height and crown area of individual trees from lidar data using an object-based method to identify individual tree crowns and estimate their biomass. The best object-based model approached the accuracy of field allometry at both the tree and plot levels, and it more than doubled the accuracy compared to existing airborne methods (17% vs. 44% deviation from harvested biomass). Allometric error accounted for less than one-third of the total residual error in airborne biomass estimates at the plot scale when using allometry with low bias. Airborne methods also gave more accurate predictions at the plot level than did field methods based on diameter-only allometry. These results provide a novel comparison of field and airborne biomass estimates using harvested plots and advance the role of lidar remote sensing in savanna ecosystems.

Unfolding Kinetics of β-Lactoglobulin Induced by Surfactant and Denaturant: A Stopped-Flow/Fluorescence Study

PubMed Central

Viseu, Maria Isabel; Melo, Eduardo P.; Carvalho, Teresa Isabel; Correia, Raquel F.; Costa, Sílvia M. B.

2007-01-01

The β→α transition of β-lactoglobulin, a globular protein abundant in the milk of several mammals, is investigated in this work. This transition, induced by the cationic surfactant dodecyltrimethylammonium chloride (DTAC), is accompanied by partial unfolding of the protein. In this work, unfolding of bovine β-lactoglobulin in DTAC is compared with its unfolding induced by the chemical denaturant guanidine hydrochloride (GnHCl). The final protein states attained in the two media have quite different secondary structure: in DTAC the α-helical content increases, leading to the so-called α-state; in GnHCl the amount of ordered secondary-structure decreases, resulting in a random coil-rich final state (denatured, or D, state). To obtain information on both mechanistic routes, in DTAC and GnHCl, and to characterize intermediates, the kinetics of unfolding were investigated in the two media. Equilibrium and kinetic data show the partial accumulation of an on-pathway intermediate in each unfolding route: in DTAC, an intermediate (I1) with mostly native secondary structure but loose tertiary structure appears between the native (β) and α-states; in GnHCl, another intermediate (I2) appears between states β and D. Kinetic rate constants follow a linear Chevron-plot representation in GnHCl, but show a more complex mechanism in DTAC, which acts like a stronger binding species. PMID:17693475

A century of enzyme kinetic analysis, 1913 to 2013.

PubMed

Johnson, Kenneth A

2013-09-02

This review traces the history and logical progression of methods for quantitative analysis of enzyme kinetics from the 1913 Michaelis and Menten paper to the application of modern computational methods today. Following a brief review of methods for fitting steady state kinetic data, modern methods are highlighted for fitting full progress curve kinetics based upon numerical integration of rate equations, including a re-analysis of the original Michaelis-Menten full time course kinetic data. Finally, several illustrations of modern transient state kinetic methods of analysis are shown which enable the elucidation of reactions occurring at the active sites of enzymes in order to relate structure and function. Copyright © 2013 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

A method for analyzing temporal patterns of variability of a time series from Poincare plots.

PubMed

Fishman, Mikkel; Jacono, Frank J; Park, Soojin; Jamasebi, Reza; Thungtong, Anurak; Loparo, Kenneth A; Dick, Thomas E

2012-07-01

The Poincaré plot is a popular two-dimensional, time series analysis tool because of its intuitive display of dynamic system behavior. Poincaré plots have been used to visualize heart rate and respiratory pattern variabilities. However, conventional quantitative analysis relies primarily on statistical measurements of the cumulative distribution of points, making it difficult to interpret irregular or complex plots. Moreover, the plots are constructed to reflect highly correlated regions of the time series, reducing the amount of nonlinear information that is presented and thereby hiding potentially relevant features. We propose temporal Poincaré variability (TPV), a novel analysis methodology that uses standard techniques to quantify the temporal distribution of points and to detect nonlinear sources responsible for physiological variability. In addition, the analysis is applied across multiple time delays, yielding a richer insight into system dynamics than the traditional circle return plot. The method is applied to data sets of R-R intervals and to synthetic point process data extracted from the Lorenz time series. The results demonstrate that TPV complements the traditional analysis and can be applied more generally, including Poincaré plots with multiple clusters, and more consistently than the conventional measures and can address questions regarding potential structure underlying the variability of a data set.

The Zombie Plot: A Simple Graphic Method for Visualizing the Efficacy of a Diagnostic Test.

PubMed

Richardson, Michael L

2016-08-09

One of the most important jobs of a radiologist is to pick the most appropriate imaging test for a particular clinical situation. Making a proper selection sometimes requires statistical analysis. The objective of this article is to introduce a simple graphic technique, an ROC plot that has been divided into zones of mostly bad imaging efficacy (ZOMBIE, hereafter referred to as the "zombie plot"), that transforms information about imaging efficacy from the numeric domain into the visual domain. The numeric rationale for the use of zombie plots is given, as are several examples of the clinical use of these plots. Two online calculators are described that simplify the process of producing a zombie plot.

Isotopic Characterisation of Methane Emissions: use of Keeling-plot Methods to Identify Source Signatures in Boreal Wetlands and Other Settings

NASA Astrophysics Data System (ADS)

Fisher, R. E.; Lowry, D.; France, J.; Lanoiselle, M.; Zazzeri, G.; Nisbet, E. G.

2012-12-01

Different methane sources have different δ13CCH4 and δDCH4 signatures, which potentially provides a powerful constraint on models of methane emission budgets. However source signatures remain poorly known and need to be studied in more detail if isotopic measurements of ambient air are to be used to constrain regional and global emissions. The Keeling plot method (plotting δ13CCH4 or δDCH4 against 1/CH4 concentration in samples of ambient air in the close vicinity of known sources) directly assesses the source signature of the methane that is actually emitted to the air. This contrasts with chamber studies, measuring air within a chamber, where local micro-meteorological and microbiological processes are occurring. Keeling plot methods have been applied to a wide variety of settings in this study. The selection of appropriate background measurements for Keeling plot analysis is also considered. The method has been used on a local scale to identify the source signature of summer emissions from subarctic wetlands in Fennoscandia. Samples are collected from low height (0.3-3m) over the wetlands during 24-hour periods, to collect daily emissions maxima (warm late afternoons), inversion maxima (at the coldest time of the 24hr daylight: usually earliest morning), and ambient minima when mixing occurs (often mid afternoon). Some results are comparable to parallel chamber studies, but in other cases there are small but significant shifts between CH4 in chamber air and CH4 that is dispersing in the above-ground air. On a regional to continental scale the isotopic signature of bulk sources of emissions can be identified using Keeling plots. The methodology is very applicable for use in urban and urban-rural settings. For example, the winter SE monsoon sweeps from inland central Asia over China to Hong Kong. Application of back trajectory analysis and Keeling plot methods implied coal emissions may be a significant Chinese source of methane in January, although in other months biological sources dominate. Similarly, in London the method has been used to test the London methane emission inventory.

Plotting Rates of Photosynthesis as a Function of Light Quantity.

ERIC Educational Resources Information Center

Dean, Rob L.

1996-01-01

Discusses methods for plotting rates of photosynthesis as a function of light quantity. Presents evidence that suggests that empirically derived conversion factors, which are used to convert foot candles to photon fluence rates, should be used with extreme caution. Suggests how rate data are best plotted when any kind of light meter is not…

Estimating mapped-plot forest attributes with ratios of means

Treesearch

S.J. Zarnoch; W.A. Bechtold

2000-01-01

The mapped-plot design utilized by the U.S. Department of Agriculture (USDA) Forest Inventory and Analysis and the National Forest Health Monitoring Programs is described. Data from 2458 forested mapped plots systematically spread across 25 States reveal that 35 percent straddle multiple conditions. The ratio-of-means estimator is developed as a method to obtain...

The Gran Plot Analysis of an Acid Mixture. An Undergraduate Experiment to Highlight this Alternate Method.

ERIC Educational Resources Information Center

Boiani, James A.

1986-01-01

Describes an experiment which uses the Gran plot for analyzing free ions as well as those involved in an equilibrium. Discusses the benefits of using Gran plots in the study of acids, as well as other analytes in solutions. Presents background theory along with a description of the experimental procedures. (TW)

Digital data collection in forest dynamics plots

Treesearch

Faith Inman-Narahari; Christian Giardina; Rebecca Ostertag; Susan Cordell; Lawren Sack

2010-01-01

Summary 1. Computers are widely used in all aspects of research but their application to in-field data collection for forest plots has rarely been evaluated. 2. We developed digital data collection methods using ESRI mapping software and ruggedized field computers to map and measure ~30 000 trees in two 4-ha forest dynamics plots in wet and dry...

Use of in situ FT-Raman spectroscopy to study the kinetics of the transformation of carbamazepine polymorphs.

PubMed

O'Brien, Laura E; Timmins, Peter; Williams, Adrian C; York, Peter

2004-10-29

The solid-state transformation of carbamazepine from form III to form I was examined by Fourier Transform Raman spectroscopy. Using a novel environmental chamber, the isothermal conversion was monitored in situ at 130 degrees C, 138 degrees C, 140 degrees C and 150 degrees C. The rate of transformation was monitored by taking the relative intensities of peaks arising from two CH bending modes; this approach minimised errors due to thermal artefacts and variations in power intensities or scattering efficiencies from the samples in which crystal habit changed from a characteristic prism morphology (form III) to whiskers (form I). The solid-state transformation at the different temperatures was fitted to various solid-state kinetic models of which four gave good fits, thus indicating the complexity of the process which is known to occur via a solid-gas-solid mechanism. Arrhenius plots from the kinetic models yielded activation energies from 344 kJ mol(-1) to 368 kJ mol(-1) for the transformation. The study demonstrates the value of a rapid in situ analysis of drug polymorphic type which can be of value for at-line in-process control.

Kinetics of Static Strain Aging in Polycrystalline NiAl-based Alloys

NASA Technical Reports Server (NTRS)

Weaver, M. L.; Kaufman, M. J.; Noebe, R. D.

1996-01-01

The kinetics of yield point return have been studied in two NiAl-based alloys as a function of aging time at temperatures between 300 and 700 K. The results indicate that the upper yield stress increment, Delta sigma(sub u) (i.e., stress difference between the upper yield point and the final flow stress achieved during prestraining), in conventional purity (CP-NiAl) and in high purity carbon-doped (NiAl-C) material first increased with a t(exp 2/3) relationship before reaching a plateau. This behavior suggests that a Cottrell locking mechanism is the cause for yield points in NiAl. In addition, positive y-axis intercepts were observed in plots of Delta sigma(sub u) versus t(exp 2/3) suggesting the operation of a Snoek mechanism. Analysis according to the Cottrell Bilby model of atmosphere formation around dislocations yields an activation energy for yield point return in the range 70 to 76 kJ/mol which is comparable to the activation energy for diffusion of interstitial impurities in bcc metals. It is, thus, concluded that the kinetics of static strain aging in NiAl are controlled by the locking of dislocations by Cottrell atmospheres of carbon atoms around dislocations.

Biomass Development in SRI Field Under Unmaintained Alternate Wetting-Drying Irrigation

NASA Astrophysics Data System (ADS)

Ardiansyah; Chusnul, A.; Krissandi, W.; Asna, M.

2018-05-01

The aim of this research is to observe biomass development of SRI on farmers practice in three plots with different level. This research observes the farmer practice of SRI and Non-SRI during the uncertainty of irrigation water supply and its effects on paddy biomass development during growth stages and final stage of crop. A farmer group that already understand the principle of SRI, applied this method into several plots of their rented paddy field. Researcher interventions were eliminated from their action, so it is purely on farmers decision on managing their SRI plots. Three plots from both SRI and Non-SRI were chosen based on the position of the plot related their access to water. First plots had direct access to water from tertiary irrigation channel (on farm). Second plots were received water from previous upper plots and drainage water into other plots. Third plots were in the bottom position, where they received water from upper plot, and drainage water into farm drainage channel. Result shows there are similar patterns of root, straw, and leaves of biomass during crop growth. On the other hand, during generative phase, grain development shows different pattern and resulting different biomass in harvest time. Second plot, (of SRI) that has water from first plot has the average of biomass grain per plant of 54.4, higher than first plot and third plot, which are 33.8 g and 38.4. Average biomass in second plot is 74.6 g, higher than first and third plot, which are 49.9 g and 52.3 g.

RADIAL FLOW PATTERN OF A SLOW CORONAL MASS EJECTION

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

Feng, Li; Gan, Weiqun, E-mail: lfeng@pmo.ac.cn; Inhester, Bernd

2015-06-01

Height–time plots of the leading edge of coronal mass ejections (CMEs) have often been used to study CME kinematics. We propose a new method to analyze the CME kinematics in more detail by determining the radial mass transport process throughout the entire CME. Thus, our method is able to estimate not only the speed of the CME front but also the radial flow speed inside the CME. We have applied this method to a slow CME with an average leading edge speed of about 480 km s{sup −1}. In the Lagrangian frame, the speeds of the individual CME mass elementsmore » stay almost constant within 2 and 15 R{sub S}, the range over which we analyzed the CME. Hence, we have no evidence of net radial forces acting on parts of the CME in this range or of a pile up of mass ahead of the CME. We find evidence that the leading edge trajectory obtained by tie-pointing may gradually lag behind the Lagrangian front-side trajectories derived from our analysis. Our results also allow a much more precise estimate of the CME energy. Compared with conventional estimates using the CME total mass and leading edge motion, we find that the latter may overestimate the kinetic energy and the gravitational potential energy.« less

Experimental conformational energy maps of proteins and peptides.

PubMed

Balaji, Govardhan A; Nagendra, H G; Balaji, Vitukudi N; Rao, Shashidhar N

2017-06-01

We have presented an extensive analysis of the peptide backbone dihedral angles in the PDB structures and computed experimental Ramachandran plots for their distributions seen under a various constraints on X-ray resolution, representativeness at different sequence identity percentages, and hydrogen bonding distances. These experimental distributions have been converted into isoenergy contour plots using the approach employed previously by F. M. Pohl. This has led to the identification of energetically favored minima in the Ramachandran (ϕ, ψ) plots in which global minima are predominantly observed either in the right-handed α-helical or the polyproline II regions. Further, we have identified low energy pathways for transitions between various minima in the (ϕ,ψ) plots. We have compared and presented the experimental plots with published theoretical plots obtained from both molecular mechanics and quantum mechanical approaches. In addition, we have developed and employed a root mean square deviation (RMSD) metric for isoenergy contours in various ranges, as a measure (in kcal.mol -1 ) to compare any two plots and determine the extent of correlation and similarity between their isoenergy contours. In general, we observe a greater degree of compatibility with experimental plots for energy maps obtained from molecular mechanics methods compared to most quantum mechanical methods. The experimental energy plots we have investigated could be helpful in refining protein structures obtained from X-ray, NMR, and electron microscopy and in refining force field parameters to enable simulations of peptide and protein structures that have higher degree of consistency with experiments. Proteins 2017; 85:979-1001. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Study of electron beam on electron cyclotron waves with AC field in the magnetosphere of Uranus

NASA Astrophysics Data System (ADS)

Kaur, Rajbir; Kumari, Jyoti; Pandey, R. S.

2018-05-01

In this paper, we deal with the oblique electromagnetic electron cyclotron (EMEC) waves in the Uranus magnetosphere. The expression of the dispersion relation is plotted by using the method of the feature solution. After the kinetic method, the growth rate and the actual frequency of the EMEC wave are studied theoretically in the Uranian system. NASA, Voyager 2, the observed results of the space detectors show that the spin axes of the planets are abnormally oriented and that there are more particles in the high energy tail of the Uranian magnetospheric plasma. Therefore, this paper uses the Kappa distribution instead of the usual Maxwell distribution. The study extends to the tilt propagation of EMEC waves, which has a change in temperature anisotropy and propagation angle with respect to the direction of the magnetic field. These parameters were found to support the growth rate of EMEC waves. However, the response of the actual frequency of these waves is not the same as the rate of growth in all cases. These results apply to the detailed comparison of planetary studies of the space plasma environment and the magnetosphere system.

Kinetics of the hydrolysis of N-benzoyl-l-serine methyl ester catalysed by bromelain and by papain. Analysis of modifier mechanisms by lattice nomography, computational methods of parameter evaluation for substrate-activated catalyses and consequences of postulated non-productive binding in bromelain- and papain-catalysed hydrolyses

PubMed Central

Wharton, Christopher W.; Cornish-Bowden, Athel; Brocklehurst, Keith; Crook, Eric M.

1974-01-01

1. N-Benzoyl-l-serine methyl ester was synthesized and evaluated as a substrate for bromelain (EC 3.4.22.4) and for papain (EC 3.4.22.2). 2. For the bromelain-catalysed hydrolysis at pH7.0, plots of [S0]/vi (initial substrate concn./initial velocity) versus [S0] are markedly curved, concave downwards. 3. Analysis by lattice nomography of a modifier kinetic mechanism in which the modifier is substrate reveals that concave-down [S0]/vi versus [S0] plots can arise when the ratio of the rate constants that characterize the breakdown of the binary (ES) and ternary (SES) complexes is either less than or greater than 1. In the latter case, there are severe restrictions on the values that may be taken by the ratio of the dissociation constants of the productive and non-productive binary complexes. 4. Concave-down [S0]/vi versus [S0] plots cannot arise from compulsory substrate activation. 5. Computational methods, based on function minimization, for determination of the apparent parameters that characterize a non-compulsory substrate-activated catalysis are described. 6. In an attempt to interpret the catalysis by bromelain of the hydrolysis of N-benzoyl-l-serine methyl ester in terms of substrate activation, the general substrate-activation model was simplified to one in which only one binary ES complex (that which gives rise directly to products) can form. 7. In terms of this model, the bromelain-catalysed hydrolysis of N-benzoyl-l-serine methyl ester at pH7.0, I=0.1 and 25°C is characterized by Km1 (the dissociation constant of ES)=1.22±0.73mm, k (the rate constant for the breakdown of ES to E+products, P)=1.57×10−2±0.32×10−2s−1, Ka2 (the dissociation constant that characterizes the breakdown of SES to ES and S)=0.38±0.06m, and k′ (the rate constant for the breakdown of SES to E+P+S)=0.45±0.04s−1. 8. These parameters are compared with those in the literature that characterize the bromelain-catalysed hydrolysis of α-N-benzoyl-l-arginine ethyl ester and of α-N-benzoyl-l-arginine amide; Km1 and k for the serine ester hydrolysis are somewhat similar to Km and kcat. for the arginine amide hydrolysis and Kas and k′ for the serine ester hydrolysis are somewhat similar to Km and kcat. for the arginine ester hydrolysis. 9. A previous interpretation of the inter-relationships of the values of kcat. and Km for the bromelain-catalysed hydrolysis of the arginine ester and amide substrates is discussed critically and an alternative interpretation involving substantial non-productive binding of the arginine amide substrate to bromelain is suggested. 10. The parameters for the bromelain-catalysed hydrolysis of the serine ester substrate are tentatively interpreted in terms of non-productive binding in the binary complex and a decrease of this type of binding by ternary complex-formation. 11. The Michaelis parameters for the papain-catalysed hydrolysis of the serine ester substrate (Km=52±4mm, kcat.=2.80±0.1s−1 at pH7.0, I=0.1, 25.0°C) are similar to those for the papain-catalysed hydrolysis of methyl hippurate. 12. Urea and guanidine hydrochloride at concentrations of 1m have only small effects on the kinetic parameters for the hydrolysis of the serine ester substrate catalysed by bromelain and by papain. PMID:4455211

An Excel macro for generating trilinear plots.

PubMed

Shikaze, Steven G; Crowe, Allan S

2007-01-01

This computer note describes a method for creating trilinear plots in Microsoft Excel. Macros have been created in MS Excel's internal language: Visual Basic for Applications (VBA). A simple form has been set up to allow the user to input data from an Excel worksheet. The VBA macro is used to convert the triangular data (which consist of three columns of percentage data) into X-Y data. The macro then generates the axes, labels, and grid for the trilinear plot. The X-Y data are plotted as scatter data in Excel. By providing this macro in Excel, users can create trilinear plots in a quick, inexpensive manner.

Relative equilibrium plot improves graphical analysis and allows bias correction of standardized uptake value ratio in quantitative 11C-PiB PET studies.

PubMed

Zhou, Yun; Sojkova, Jitka; Resnick, Susan M; Wong, Dean F

2012-04-01

Both the standardized uptake value ratio (SUVR) and the Logan plot result in biased distribution volume ratios (DVRs) in ligand-receptor dynamic PET studies. The objective of this study was to use a recently developed relative equilibrium-based graphical (RE) plot method to improve and simplify the 2 commonly used methods for quantification of (11)C-Pittsburgh compound B ((11)C-PiB) PET. The overestimation of DVR in SUVR was analyzed theoretically using the Logan and the RE plots. A bias-corrected SUVR (bcSUVR) was derived from the RE plot. Seventy-eight (11)C-PiB dynamic PET scans (66 from controls and 12 from participants with mild cognitive impaired [MCI] from the Baltimore Longitudinal Study of Aging) were acquired over 90 min. Regions of interest (ROIs) were defined on coregistered MR images. Both the ROI and the pixelwise time-activity curves were used to evaluate the estimates of DVR. DVRs obtained using the Logan plot applied to ROI time-activity curves were used as a reference for comparison of DVR estimates. Results from the theoretic analysis were confirmed by human studies. ROI estimates from the RE plot and the bcSUVR were nearly identical to those from the Logan plot with ROI time-activity curves. In contrast, ROI estimates from DVR images in frontal, temporal, parietal, and cingulate regions and the striatum were underestimated by the Logan plot (controls, 4%-12%; MCI, 9%-16%) and overestimated by the SUVR (controls, 8%-16%; MCI, 16%-24%). This bias was higher in the MCI group than in controls (P < 0.01) but was not present when data were analyzed using either the RE plot or the bcSUVR. The RE plot improves pixelwise quantification of (11)C-PiB dynamic PET, compared with the conventional Logan plot. The bcSUVR results in lower bias and higher consistency of DVR estimates than of SUVR. The RE plot and the bcSUVR are practical quantitative approaches that improve the analysis of (11)C-PiB studies.

Nebraska's forests, 2005: statistics, methods, and quality assurance

Treesearch

Patrick D. Miles; Dacia M. Meneguzzo; Charles J. Barnett

2011-01-01

The first full annual inventory of Nebraska's forests was completed in 2005 after 8,335 plots were selected and 274 forested plots were visited and measured. This report includes detailed information on forest inventory methods, and data quality estimates. Tables of various important resource statistics are presented. Detailed analysis of the inventory data are...

Kansas's forests, 2005: statistics, methods, and quality assurance

Treesearch

Patrick D. Miles; W. Keith Moser; Charles J. Barnett

2011-01-01

The first full annual inventory of Kansas's forests was completed in 2005 after 8,868 plots were selected and 468 forested plots were visited and measured. This report includes detailed information on forest inventory methods and data quality estimates. Important resource statistics are included in the tables. A detailed analysis of Kansas inventory is presented...

The diagnostic plot analysis of artesian aquifers with case studies in Table Mountain Group of South Africa

NASA Astrophysics Data System (ADS)

Sun, Xiaobin; Xu, Yongxin; Lin, Lixiang

2015-05-01

Parameter estimates of artesian aquifers where piezometric head is above ground level are largely made through free-flowing and recovery tests. The straight-line method proposed by Jacob-Lohman is often used for interpretation of flow rate measured at flowing artesian boreholes. However, the approach fails to interpret the free-flowing test data from two artesian boreholes in the fractured-rock aquifer in Table Mountain Group (TMG) of South Africa. The diagnostic plot method using the reciprocal rate derivative is adapted to evaluate the artesian aquifer properties. The variation of the derivative helps not only identify flow regimes and discern the boundary conditions, but also facilitates conceptualization of the aquifer system and selection of an appropriate model for data interpretation later on. Test data from two free-flowing tests conducted in different sites in TMG are analysed using the diagnostic plot method. Based on the results, conceptual models and appropriate approaches are developed to evaluate the aquifer properties. The advantages and limitations of using the diagnostic plot method on free-flowing test data are discussed.

A Mesh Refinement Study on the Impact Response of a Shuttle Leading-Edge Panel Finite Element Simulation

NASA Technical Reports Server (NTRS)

Fasanella, Edwin L.; Jackson, Karen E.; Lyle, Karen H.; Spellman, Regina L.

2006-01-01

A study was performed to examine the influence of varying mesh density on an LS-DYNA simulation of a rectangular-shaped foam projectile impacting the space shuttle leading edge Panel 6. The shuttle leading-edge panels are fabricated of reinforced carbon-carbon (RCC) material. During the study, nine cases were executed with all possible combinations of coarse, baseline, and fine meshes of the foam and panel. For each simulation, the same material properties and impact conditions were specified and only the mesh density was varied. In the baseline model, the shell elements representing the RCC panel are approximately 0.2-in. on edge, whereas the foam elements are about 0.5-in. on edge. The element nominal edge-length for the baseline panel was halved to create a fine panel (0.1-in. edge length) mesh and doubled to create a coarse panel (0.4-in. edge length) mesh. In addition, the element nominal edge-length of the baseline foam projectile was halved (0.25-in. edge length) to create a fine foam mesh and doubled (1.0-in. edge length) to create a coarse foam mesh. The initial impact velocity of the foam was 775 ft/s. The simulations were executed in LS-DYNA for 6 ms of simulation time. Contour plots of resultant panel displacement and effective stress in the foam were compared at four discrete time intervals. Also, time-history responses of internal and kinetic energy of the panel, kinetic and hourglass energy of the foam, and resultant contact force were plotted to determine the influence of mesh density.

Folding domain B of protein A on a dynamically partitioned free energy landscape.

PubMed

Nelson, Erik D; Grishin, Nick V

2008-02-05

The B domain of staphylococcal protein A (BdpA) is a small helical protein that has been studied intensively in kinetics experiments and detailed computer simulations that include explicit water. The simulations indicate that BdpA needs to reorganize in crossing the transition barrier to facilitate folding its C-terminal helix (H3) onto the nucleus formed from helices H1 and H2. This process suggests frustration between two partially ordered forms of the protein, but recent varphi value measurements indicate that the transition structure is relatively constant over a broad range of temperatures. Here we develop a simplistic model to investigate the folding transition in which properties of the free energy landscape can be quantitatively compared with experimental data. The model is a continuation of the Muñoz-Eaton model to include the intermittency of contacts between structured parts of the protein, and the results compare variations in the landscape with denaturant and temperature to varphi value measurements and chevron plots of the kinetic rates. The topography of the model landscape (in particular, the feature of frustration) is consistent with detailed simulations even though variations in the varphi values are close to measured values. The transition barrier is smaller than indicated by the chevron data, but it agrees in order of magnitude with a similar alpha-carbon type of model. Discrepancies with the chevron plots are investigated from the point of view of solvent effects, and an approach is suggested to account for solvent participation in the model.

Predicting rainfall erosivity by momentum and kinetic energy in Mediterranean environment

NASA Astrophysics Data System (ADS)

Carollo, Francesco G.; Ferro, Vito; Serio, Maria A.

2018-05-01

Rainfall erosivity is an index that describes the power of rainfall to cause soil erosion and it is used around the world for assessing and predicting soil loss on agricultural lands. Erosivity can be represented in terms of both rainfall momentum and kinetic energy, both calculated per unit time and area. Contrasting results on the representativeness of these two variables are available: some authors stated that momentum and kinetic energy are practically interchangeable in soil loss estimation while other found that kinetic energy is the most suitable expression of rainfall erosivity. The direct and continuous measurements of momentum and kinetic energy by a disdrometer allow also to establish a relationship with rainfall intensity at the study site. At first in this paper a comparison between the momentum-rainfall intensity relationships measured at Palermo and El Teularet by an optical disdrometer is presented. For a fixed rainfall intensity the measurements showed that the rainfall momentum values measured at the two experimental sites are not coincident. However both datasets presented a threshold value of rainfall intensity over which the rainfall momentum assumes a quasi-constant value. Then the reliability of a theoretically deduced relationship, linking momentum, rainfall intensity and median volume diameter, is positively verified using measured raindrop size distributions. An analysis to assess which variable, momentum or kinetic energy per unit area and time, is the best predictor of erosivity in Italy and Spain was also carried out. This investigation highlighted that the rainfall kinetic energy per unit area and time can be substituted by rainfall momentum as index for estimating the rainfall erosivity, and this result does not depend on the site where precipitation occurs. Finally, rainfall intensity measurements and soil loss data collected from the bare plots equipped at Sparacia experimental area were used to verify the reliability of some rainfall erosivity indices and their ability to distinguish the type of involved soil erosion processes.

The relative importance of decomposition and transport mechanisms in accounting for soil organic carbon profiles

NASA Astrophysics Data System (ADS)

Guenet, B.; Eglin, T.; Vasilyeva, N.; Peylin, P.; Ciais, P.; Chenu, C.

2013-04-01

Soil is the major terrestrial reservoir of carbon and a substantial part of this carbon is stored in deep layers, typically deeper than 50 cm below the surface. Several studies underlined the quantitative importance of this deep soil organic carbon (SOC) pool and models are needed to better understand this stock and its evolution under climate and land-uses changes. In this study, we tested and compared three simple theoretical models of vertical transport for SOC against SOC profiles measurements from a long-term bare fallow experiment carried out by the Central-Chernozem State Natural Biosphere Reserve in the Kursk Region of Russia. The transport schemes tested are diffusion, advection and both diffusion and advection. They are coupled to three different formulations of soil carbon decomposition kinetics. The first formulation is a first order kinetics widely used in global SOC decomposition models; the second one, so-called "priming" model, links SOC decomposition rate to the amount of fresh organic matter, representing the substrate interactions. The last one is also a first order kinetics, but SOC is split into two pools. Field data are from a set of three bare fallow plots where soil received no input during the past 20, 26 and 58 yr, respectively. Parameters of the models were optimised using a Bayesian method. The best results are obtained when SOC decomposition is assumed to be controlled by fresh organic matter (i.e., the priming model). In comparison to the first-order kinetic model, the priming model reduces the overestimation in the deep layers. We also observed that the transport scheme that improved the fit with the data depended on the soil carbon mineralisation formulation chosen. When soil carbon decomposition was modelled to depend on the fresh organic matter amount, the transport mechanism which improved best the fit to the SOC profile data was the model representing both advection and diffusion. Interestingly, the older the bare fallow is, the lesser the need for diffusion is, suggesting that stabilised carbon may not be transported within the profile by the same mechanisms than more labile carbon.

[Metabolic kinetics of MN9202 in Beagle dog liver microsomes].

PubMed

Yang, Zhi-fu; Zhou, Si-yuan; Mei, Qi-bing; Yang, Tie-hong; Liu, Zhen-guo

2005-11-01

To study the metabolic kinetics of MN9202 in Beagle dog liver microsome. Beagle dog liver microsomes were prepared by using ultracentrifuge method. After incubating 0.4 micromol x L(-1) MN9202 with 1 g x L(-1) microsomes for 30 min at 37 degrees C, the reaction was terminated by adding 0.5 mL alkalization. The RP-HPLC was used to determine the drug in the incubation mixture. The Michaelis-Menten parameters Km, and Vmax in Beagle dog liver microsomes were initially estimated by analyzing Lineweave-Brurk plot. Various selective CYP inhibitors were used to investigate their inhibitory effect on the metabolism of MN9202. The Km, Vmax and CLint of MN9202 were (22.6 +/- 8.0) micromol x L(-1), (0.54 +/- 0.17) micromol x g(-1) x min(-1) and (0.0242 +/- 0.0009) L x g(-1) x min(-1), respectively. The metabolism of MN9202 was significantly inhibited by ketoconazole (Ket) and troleandomycin (Tro) in Beagle dog liver microsomes. Tranylcypromine (Tra) could inhibit the metabolism of drug as well. While other inhibitors showed little inhibitory effect on the metabolism of MN9202. It was shown that CYP3A and CYP2C19 were involved in MN9202 metabolism. The inhibitors of human CYP3A and CYP2C19 may have potential interaction with MN9202, and this can reduce the metabolism rate and increase the toxicity of MN9202.

A Deep Insight into the Details of the Interisomerization and Decomposition Mechanism of o-Quinolyl and o-Isoquinolyl Radicals. Quantum Chemical Calculations and Computer Modeling.

PubMed

Dubnikova, Faina; Tamburu, Carmen; Lifshitz, Assa

2016-09-29

The isomerization of o-quinolyl ↔ o-isoquinolyl radicals and their thermal decomposition were studied by quantum chemical methods, where potential energy surfaces of the reaction channels and their kinetics rate parameters were determined. A detailed kinetics scheme containing 40 elementary steps was constructed. Computer simulations were carried out to determine the isomerization mechanism and the distribution of reaction products in the decomposition. The calculated mole percent of the stable products was compared to the experimental values that were obtained in this laboratory in the past, using the single pulse shock tube. The agreement between the experimental and the calculated mole percents was very good. A map of the figures containing the mole percent's of eight stable products of the decomposition plotted vs T are presented. The fast isomerization of o-quinolyl → o-isoquinolyl radicals via the intermediate indene imine radical and the attainment of fast equilibrium between these two radicals is the reason for the identical product distribution regardless whether the reactant radical is o-quinolyl or o-isoquinolyl. Three of the main decomposition products of o-quinolyl radical, are those containing the benzene ring, namely, phenyl, benzonitrile, and phenylacetylene radicals. They undergo further decomposition mainly at high temperatures via two types of reactions: (1) Opening of the benzene ring in the radicals, followed by splitting into fragments. (2) Dissociative attachment of benzonitrile and phenyl acetylene by hydrogen atoms to form hydrogen cyanide and acetylene.

Seedbed treatment increases dominance of natural loblolly pine reproduction

Treesearch

S. Little; J. J. Mohr

1957-01-01

In 1951 a 30-acre mature stand of loblolly pine on Maryland's Eastern Shore was cut, leaving 10 pine seed trees per acre; and three different methods of seedbed preparation were tried on experimental plots within the stand. Besides a control plot, which was only logged, the plot treatments included: (a) pulling a stump with a small bulldozer before cutting,...

Multiscale Poincaré plots for visualizing the structure of heartbeat time series.

PubMed

Henriques, Teresa S; Mariani, Sara; Burykin, Anton; Rodrigues, Filipa; Silva, Tiago F; Goldberger, Ary L

2016-02-09

Poincaré delay maps are widely used in the analysis of cardiac interbeat interval (RR) dynamics. To facilitate visualization of the structure of these time series, we introduce multiscale Poincaré (MSP) plots. Starting with the original RR time series, the method employs a coarse-graining procedure to create a family of time series, each of which represents the system's dynamics in a different time scale. Next, the Poincaré plots are constructed for the original and the coarse-grained time series. Finally, as an optional adjunct, color can be added to each point to represent its normalized frequency. We illustrate the MSP method on simulated Gaussian white and 1/f noise time series. The MSP plots of 1/f noise time series reveal relative conservation of the phase space area over multiple time scales, while those of white noise show a marked reduction in area. We also show how MSP plots can be used to illustrate the loss of complexity when heartbeat time series from healthy subjects are compared with those from patients with chronic (congestive) heart failure syndrome or with atrial fibrillation. This generalized multiscale approach to Poincaré plots may be useful in visualizing other types of time series.

A comparison of the abilities of the USLE-M, RUSLE2 and WEPP to model event erosion from bare fallow areas.

PubMed

Kinnell, P I A

2017-10-15

Traditionally, the Universal Soil Loss Equation (USLE) and the revised version of it (RUSLE) have been applied to predicting the long term average soil loss produced by rainfall erosion in many parts of the world. Overtime, it has been recognized that there is a need to predict soil losses over shorter time scales and this has led to the development of WEPP and RUSLE2 which can be used to predict soil losses generated by individual rainfall events. Data currently exists that enables the RUSLE2, WEPP and the USLE-M to estimate historic soil losses from bare fallow runoff and soil loss plots recorded in the USLE database. Comparisons of the abilities of the USLE-M and RUSLE2 to estimate event soil losses from bare fallow were undertaken under circumstances where both models produced the same total soil loss as observed for sets of erosion events on 4 different plots at 4 different locations. Likewise, comparisons of the abilities of the USLE-M and WEPP to model event soil loss from bare fallow were undertaken for sets of erosion events on 4 plots at 4 different locations. Despite being calibrated specifically for each plot, WEPP produced the worst estimates of event soil loss for all the 4 plots. Generally, the USLE-M using measured runoff to calculate the product of the runoff ratio, storm kinetic energy and the maximum 30-minute rainfall intensity produced the best estimates. As to be expected, ability of the USLE-M to estimate event soil loss was reduced when runoff predicted by either RUSLE2 or WEPP was used. Despite this, the USLE-M using runoff predicted by WEPP estimated event soil loss better than WEPP. RUSLE2 also outperformed WEPP. Copyright © 2017 Elsevier B.V. All rights reserved.

Nonlinear Dot Plots.

PubMed

Rodrigues, Nils; Weiskopf, Daniel

2018-01-01

Conventional dot plots use a constant dot size and are typically applied to show the frequency distribution of small data sets. Unfortunately, they are not designed for a high dynamic range of frequencies. We address this problem by introducing nonlinear dot plots. Adopting the idea of nonlinear scaling from logarithmic bar charts, our plots allow for dots of varying size so that columns with a large number of samples are reduced in height. For the construction of these diagrams, we introduce an efficient two-way sweep algorithm that leads to a dense and symmetrical layout. We compensate aliasing artifacts at high dot densities by a specifically designed low-pass filtering method. Examples of nonlinear dot plots are compared to conventional dot plots as well as linear and logarithmic histograms. Finally, we include feedback from an expert review.

Vegetation resurvey is robust to plot location uncertainty

PubMed Central

Kopecký, Martin; Macek, Martin

2017-01-01

Aim Resurveys of historical vegetation plots are increasingly used for the assessment of decadal changes in plant species diversity and composition. However, historical plots are usually relocated only approximately. This potentially inflates temporal changes and undermines results. Location Temperate deciduous forests in Central Europe. Methods To explore if robust conclusions can be drawn from resurvey studies despite location uncertainty, we compared temporal changes in species richness, frequency, composition and compositional heterogeneity between exactly and approximately relocated plots. We hypothesized that compositional changes should be lower and changes in species richness should be less variable on exactly relocated plots, because pseudo-turnover inflates temporal changes on approximately relocated plots. Results Temporal changes in species richness were not more variable and temporal changes in species composition and compositional heterogeneity were not higher on approximately relocated plots. Moreover, the frequency of individual species changed similarly on both plot types. Main conclusions The resurvey of historical vegetation plots is robust to uncertainty in original plot location and, when done properly, provides reliable evidence of decadal changes in plant communities. This provides important background for other resurvey studies and opens up the possibility for large-scale assessments of plant community change. PMID:28503083

Comparative evaluation of bioactivity of crystalline trypsin for drying by Fourier-transformed infrared spectroscopy.

PubMed

Otsuka, Makoto; Fukui, Yuya; Ozaki, Yukihiro

2009-03-01

The purpose of this study was to evaluate the enzymatic stability of colloidal trypsin powder during heating in a solid-state by using Fourier transform infrared (FT-IR) spectra with chemoinformatics and generalized two-dimensional (2D) correlation spectroscopy. Colloidal crystalline trypsin powders were heated using differential scanning calorimetry. The enzymatic activity of trypsin was assayed by the kinetic degradation method. Spectra of 10 calibration sample sets were recorded three times with a FT-IR spectrometer. The maximum intensity at 1634cm(-1) of FT-IR spectra and enzymatic activity of trypsin decreased as the temperature increased. The FT-IR spectra of trypsin samples were analyzed by a principal component regression analysis (PCR). A plot of the calibration data obtained was made between the actual and predicted trypsin activity based on a two-component model with gamma(2)=0.962. On the other hand, a 2D method was applied to FT-IR spectra of heat-treated trypsin. The result was consistent with that of the chemoinformetrical method. The results for deactivation of colloidal trypsin powder by heat-treatment indicated that nano-structure of crystalline trypsin changed by heating reflecting that the beta-sheet was mainly transformed, since the peak at 1634cm(-1) decreased with dehydration. The FT-IR chemoinformetrical method allows for a solid-state quantitative analysis of the bioactivity of the bulk powder of trypsin during drying.

A new improved graphical and quantitative method for detecting bias in meta-analysis.

PubMed

Furuya-Kanamori, Luis; Barendregt, Jan J; Doi, Suhail A R

2018-04-04

Detection of publication and related biases remains suboptimal and threatens the validity and interpretation of meta-analytical findings. When bias is present, it usually differentially affects small and large studies manifesting as an association between precision and effect size and therefore visual asymmetry of conventional funnel plots. This asymmetry can be quantified and Egger's regression is, by far, the most widely used statistical measure for quantifying funnel plot asymmetry. However, concerns have been raised about both the visual appearance of funnel plots and the sensitivity of Egger's regression to detect such asymmetry, particularly when the number of studies is small. In this article, we propose a new graphical method, the Doi plot, to visualize asymmetry and also a new measure, the LFK index, to detect and quantify asymmetry of study effects in Doi plots. We demonstrate that the visual representation of asymmetry was better for the Doi plot when compared with the funnel plot. We also show that the diagnostic accuracy of the LFK index in discriminating between asymmetry due to simulated publication bias versus chance or no asymmetry was also better with the LFK index which had areas under the receiver operating characteristic curve of 0.74-0.88 with simulations of meta-analyses with five, 10, 15, and 20 studies. The Egger's regression result had lower areas under the receiver operating characteristic curve values of 0.58-0.75 across the same simulations. The LFK index also had a higher sensitivity (71.3-72.1%) than the Egger's regression result (18.5-43.0%). We conclude that the methods proposed in this article can markedly improve the ability of researchers to detect bias in meta-analysis.

Interpreting Medical Information Using Machine Learning and Individual Conditional Expectation.

PubMed

Nohara, Yasunobu; Wakata, Yoshifumi; Nakashima, Naoki

2015-01-01

Recently, machine-learning techniques have spread many fields. However, machine-learning is still not popular in medical research field due to difficulty of interpreting. In this paper, we introduce a method of interpreting medical information using machine learning technique. The method gave new explanation of partial dependence plot and individual conditional expectation plot from medical research field.

Fire Behavior (FB)

Treesearch

Robert E. Keane

2006-01-01

The Fire Behavior (FB) method is used to describe the behavior of the fire and the ambient weather and fuel conditions that influence the fire behavior. Fire behavior methods are not plot based and are collected by fire event and time-date. In general, the fire behavior data are used to interpret the fire effects documented in the plot-level sampling. Unlike the other...

North Dakota's forests, 2005: statistics, methods, and quality assurance

Treesearch

Patrick D. Miles; David E. Haugen; Charles J. Barnett

2011-01-01

The first full annual inventory of North Dakota's forests was completed in 2005 after 7,622 plots were selected and 164 forested plots were visited and measured. This report includes detailed information on forest inventory methods and data quality estimates. Important resource statistics are included in the tables. A detailed analysis of the North Dakota...

South Dakota's forests, 2005: statistics, methods, and quality assurance

Treesearch

Patrick D. Miles; Ronald J. Piva; Charles J. Barnett

2011-01-01

The first full annual inventory of South Dakota's forests was completed in 2005 after 8,302 plots were selected and 325 forested plots were visited and measured. This report includes detailed information on forest inventory methods and data quality estimates. Important resource statistics are included in the tables. A detailed analysis of the South Dakota...

Path Analysis and Residual Plotting as Methods of Environmental Scanning in Higher Education: An Illustration with Applications and Enrollments.

ERIC Educational Resources Information Center

Morcol, Goktug; McLaughlin, Gerald W.

1990-01-01

The study proposes using path analysis and residual plotting as methods supporting environmental scanning in strategic planning for higher education institutions. Path models of three levels of independent variables are developed. Dependent variables measuring applications and enrollments at Virginia Polytechnic Institute and State University are…

A Simple Method for Reproducing Orbital Plots for Illustration Using Microsoft Paint and Microsoft Excel

NASA Astrophysics Data System (ADS)

Niebuhr, Cole

2018-04-01

Papers published in the astronomical community, particularly in the field of double star research, often contain plots that display the positions of the component stars relative to each other on a Cartesian coordinate plane. Due to the complexities of plotting a three-dimensional orbit into a two-dimensional image, it is often difficult to include an accurate reproduction of the orbit for comparison purposes. Methods to circumvent this obstacle do exist; however, many of these protocols result in low-quality blurred images or require specific and often expensive software. Here, a method is reported using Microsoft Paint and Microsoft Excel to produce high-quality images with an accurate reproduction of a partial orbit.

Recurrence Density Enhanced Complex Networks for Nonlinear Time Series Analysis

NASA Astrophysics Data System (ADS)

Costa, Diego G. De B.; Reis, Barbara M. Da F.; Zou, Yong; Quiles, Marcos G.; Macau, Elbert E. N.

We introduce a new method, which is entitled Recurrence Density Enhanced Complex Network (RDE-CN), to properly analyze nonlinear time series. Our method first transforms a recurrence plot into a figure of a reduced number of points yet preserving the main and fundamental recurrence properties of the original plot. This resulting figure is then reinterpreted as a complex network, which is further characterized by network statistical measures. We illustrate the computational power of RDE-CN approach by time series by both the logistic map and experimental fluid flows, which show that our method distinguishes different dynamics sufficiently well as the traditional recurrence analysis. Therefore, the proposed methodology characterizes the recurrence matrix adequately, while using a reduced set of points from the original recurrence plots.

The quartile benefit plot: a middle ear surgery benefit assessment scheme.

PubMed

Schmerber, Sébastien; Karkas, Alexandre; Righini, Christian A; Chahine, Karim A

2008-05-01

The purpose of this study is to present a new method for the assessment of hearing improvement following stapes surgery, taking into account additional, previously omitted evaluation criteria. Retrospective. A quartile plot, based on the currently used Glasgow benefit plot, is structured to include two additional criteria of hearing assessment, namely the absence of postoperative sensorineural hearing loss and the closure of the air-bone gap to <10 dB. Pre- and postoperative hearing results of 132 patients diagnosed with bilateral otosclerosis and treated with bilateral stapes surgery were plotted on both the classical Glasgow benefit plot and the new quartile benefit plot. The difference in success assessment due to stricter assessment criteria is demonstrated. Functional success rate following bilateral stapes surgery as plotted on the traditional Glasgow benefit plot was 51.5%. Success rate for bilateral stapes surgery assessed on the new quartile plot with the addition of the two new criteria was 38.64%. The difference in success rates was found to be statistically significant. The basis of benefit assessment in stapes surgery solely on the mean deficit in air conduction results in overestimation of success rate. This study demonstrates that results that appear satisfactory when judged by the Glasgow benefit plot are of modest success when assessed by the new quartile plot. The quartile benefit plot presented in this paper provides a strict measure of presentation and evaluation of stapes surgery results.

Automated matching of multiple terrestrial laser scans for stem mapping without the use of artificial references

NASA Astrophysics Data System (ADS)

Liu, Jingbin; Liang, Xinlian; Hyyppä, Juha; Yu, Xiaowei; Lehtomäki, Matti; Pyörälä, Jiri; Zhu, Lingli; Wang, Yunsheng; Chen, Ruizhi

2017-04-01

Terrestrial laser scanning has been widely used to analyze the 3D structure of a forest in detail and to generate data at the level of a reference plot for forest inventories without destructive measurements. Multi-scan terrestrial laser scanning is more commonly applied to collect plot-level data so that all of the stems can be detected and analyzed. However, it is necessary to match the point clouds of multiple scans to yield a point cloud with automated processing. Mismatches between datasets will lead to errors during the processing of multi-scan data. Classic registration methods based on flat surfaces cannot be directly applied in forest environments; therefore, artificial reference objects have conventionally been used to assist with scan matching. The use of artificial references requires additional labor and expertise, as well as greatly increasing the cost. In this study, we present an automated processing method for plot-level stem mapping that matches multiple scans without artificial references. In contrast to previous studies, the registration method developed in this study exploits the natural geometric characteristics among a set of tree stems in a plot and combines the point clouds of multiple scans into a unified coordinate system. Integrating multiple scans improves the overall performance of stem mapping in terms of the correctness of tree detection, as well as the bias and the root-mean-square errors of forest attributes such as diameter at breast height and tree height. In addition, the automated processing method makes stem mapping more reliable and consistent among plots, reduces the costs associated with plot-based stem mapping, and enhances the efficiency.

Texture Analysis of Recurrence Plots Based on Wavelets and PSO for Laryngeal Pathologies Detection.

PubMed

Souza, Taciana A; Vieira, Vinícius J D; Correia, Suzete E N; Costa, Silvana L N C; de A Costa, Washington C; Souza, Micael A

2015-01-01

This paper deals with the discrimination between healthy and pathological speech signals using recurrence plots and wavelet transform with texture features. Approximation and detail coefficients are obtained from the recurrence plots using Haar wavelet transform, considering one decomposition level. The considered laryngeal pathologies are: paralysis, Reinke's edema and nodules. Accuracy rates above 86% were obtained by means of the employed method.

Effects of hardwood retention, season of year, and landform on the perceived scenic beauty of forest plots in the Ouachita Mountains

Treesearch

James H. Gramann; Victor A. Rudis

1994-01-01

Results from a study of the within-stand visual effects of alternative reproduction cutting methods on 20 experimental plots in the Ouachita National Forest are presented. Treatments varied in their level of hardwood retention from complete suppression of hardwoods to retention of 30 ft2/acre of basal area. Using color transparency film, plots...

Dalitz Plot Analyses of B- to D+ Pi- Pi-, B+ to Pi+ Pi- Pi+ and D(S)+ to Pi+ Pi- Pi+ at BaBar

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

Dong, Liaoyuan; /Iowa State U.

We report on the Dalitz plot analyses of B{sup -} {yields} D{sup +}{pi}{sup -}{pi}{sup -}, B{sup +} {yields} {pi}{sup +}{pi}{sup -}{pi}{sup +} and D{sub s}{sup +} {yields} {pi}{sup +}{pi}{sup -}{sup +}. The Dalitz plot method and the most recent BABAR results are discussed.

Infiltration and Runoff Measurements on Steep Burned Hillslopes Using a Rainfall Simulator with Variable Rain Intensities

USGS Publications Warehouse

Kinner, David A.; Moody, John A.

2008-01-01

Multiple rainfall intensities were used in rainfall-simulation experiments designed to investigate the infiltration and runoff from 1-square-meter plots on burned hillslopes covered by an ash layer of varying thickness. The 1-square-meter plots were on north- and south-facing hillslopes in an area burned by the Overland fire northwest of Boulder near Jamestown on the Front Range of Colorado. A single-nozzle, wide-angle, multi-intensity rain simulator was developed to investigate the infiltration and runoff on steep (30- to 40-percent gradient) burned hillslopes covered with ash. The simulated rainfall was evaluated for spatial variability, drop size, and kinetic energy. Fourteen rainfall simulations, at three intensities (about 20 millimeters per hour [mm/h], 35 mm/h, and 50 mm/h), were conducted on four plots. Measurements during and after the simulations included runoff, rainfall, suspended-sediment concentrations, surface ash layer thickness, soil moisture, soil grain size, soil lost on ignition, and plot topography. Runoff discharge reached a steady state within 7 to 26 minutes. Steady infiltration rates with the 50-mm/h application rainfall intensity approached 20?35 mm/h. If these rates are projected to rainfall application intensities used in many studies of burned area runoff production (about 80 mm/h), the steady discharge rates are on the lower end of measurements from other studies. Experiments using multiple rainfall intensities (three) suggest that runoff begins at rainfall intensities around 20 mm/h at the 1-square-meter scale, an observation consistent with a 10-mm/h rainfall intensity threshold needed for runoff initiation that has been reported in the literature.

Kinetics of Cathode Processes in Separation of Thorium from Molten Salts. Part I. Investigation of ThF$sub 4$ and ThF$sub 4$-CaF$sub 2$; KINETYKA PROCESU KATODOWEGO PRZY OSADZANIU TORU ZE STOPIONYCH SOLI. CZESC I. BADANIA ThF$sub 4$ I ThF$sub 4$-CaF$sub 2$

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

Mints, S.; Rafal'skii, V.

1961-09-01

The current-intensity curves of non-electrolyzed salts and the curves of time-intensity and current-intensity in electrolyzed salts were plotted for molten ThF/sub 4/ and ThF /sub 4/CaF/sub 2/. The intensity of salt disintegration was determined, and electric conductivity in electrolyte was observed. (trauth)

Fundamental studies on the metal chloride cathodes in sodium batteries

NASA Technical Reports Server (NTRS)

Ratnakumar, B. V.; Attia, A.; Halpert, G.

1990-01-01

The authors report studies of the passivation of the NiCl2 electrode during reduction, its effect on the electrochemical rate kinetics for the reduction, and its dependence on the state of charge of the electrode. NiCl2 exhibits passive behavior more readily at lower states of charge due to a decrease in the electrochemical area, resulting from NaCl deposited during reduction. The passive behavior is evident from the DC polarization curves as well as AC impedance plots at the same potentials, implying a correlation between them. The results of the studies are presented in detail.

Examination of the Mechanism of Rh2(II)-Catalyzed Carbazole Formation Using Intramolecular Competition Experiments

PubMed Central

Stokes, Benjamin J.; Richert, Kathleen J.; Driver, Tom G.

2009-01-01

The use of a rhodium(II) carboxylate catalyst enables the mild and stereoselective formation of carbazoles from biaryl azides. Intramolecular competition experiments of triaryl azides suggested the source of the selectivity. A primary intramolecular kinetic isotope effect was not observed and correlation of the product ratios with Hammett σ+-values produced a plot with two intersecting lines with opposite ρ-values. These data suggest that electronic donation by the biaryl π-system accelerates the formation of rhodium nitrenoid and that C–N bond formation occurs through a 4π-electron-5-atom electrocyclization. PMID:19663433

Proceedings of the Conference on the Environmental Chemistry of Hydrazine Fuels (3rd) Held in Panama City Beach, Florida on 15-17 September 1987

DTIC Science & Technology

1988-01-01

for hydrauine, MMH and UDMH are 4.78 x 10-6, 10.2 x 10Ś, and 3.19 x 10-6 aecŕ, respectively. Plots of the log(area) versus time were linear and...followed first-order kinetics except for hydrauine, for which a non- linear portion was observed in the first 6 to 8 hours. This portion of the decay...As a result, the prototype flow reactor can be represented to good approximation by a linear combination of point source solutions (Reference 19). The

Unbalanced and Minimal Point Equivalent Estimation Second-Order Split-Plot Designs

NASA Technical Reports Server (NTRS)

Parker, Peter A.; Kowalski, Scott M.; Vining, G. Geoffrey

2007-01-01

Restricting the randomization of hard-to-change factors in industrial experiments is often performed by employing a split-plot design structure. From an economic perspective, these designs minimize the experimental cost by reducing the number of resets of the hard-to- change factors. In this paper, unbalanced designs are considered for cases where the subplots are relatively expensive and the experimental apparatus accommodates an unequal number of runs per whole-plot. We provide construction methods for unbalanced second-order split- plot designs that possess the equivalence estimation optimality property, providing best linear unbiased estimates of the parameters; independent of the variance components. Unbalanced versions of the central composite and Box-Behnken designs are developed. For cases where the subplot cost approaches the whole-plot cost, minimal point designs are proposed and illustrated with a split-plot Notz design.

A Sensitive and Robust Enzyme Kinetic Experiment Using Microplates and Fluorogenic Ester Substrates

ERIC Educational Resources Information Center

Johnson, R. Jeremy; Hoops, Geoffrey C.; Savas, Christopher J.; Kartje, Zachary; Lavis, Luke D.

2015-01-01

Enzyme kinetics measurements are a standard component of undergraduate biochemistry laboratories. The combination of serine hydrolases and fluorogenic enzyme substrates provides a rapid, sensitive, and general method for measuring enzyme kinetics in an undergraduate biochemistry laboratory. In this method, the kinetic activity of multiple protein…

How to regress and predict in a Bland-Altman plot? Review and contribution based on tolerance intervals and correlated-errors-in-variables models.

PubMed

Francq, Bernard G; Govaerts, Bernadette

2016-06-30

Two main methodologies for assessing equivalence in method-comparison studies are presented separately in the literature. The first one is the well-known and widely applied Bland-Altman approach with its agreement intervals, where two methods are considered interchangeable if their differences are not clinically significant. The second approach is based on errors-in-variables regression in a classical (X,Y) plot and focuses on confidence intervals, whereby two methods are considered equivalent when providing similar measures notwithstanding the random measurement errors. This paper reconciles these two methodologies and shows their similarities and differences using both real data and simulations. A new consistent correlated-errors-in-variables regression is introduced as the errors are shown to be correlated in the Bland-Altman plot. Indeed, the coverage probabilities collapse and the biases soar when this correlation is ignored. Novel tolerance intervals are compared with agreement intervals with or without replicated data, and novel predictive intervals are introduced to predict a single measure in an (X,Y) plot or in a Bland-Atman plot with excellent coverage probabilities. We conclude that the (correlated)-errors-in-variables regressions should not be avoided in method comparison studies, although the Bland-Altman approach is usually applied to avert their complexity. We argue that tolerance or predictive intervals are better alternatives than agreement intervals, and we provide guidelines for practitioners regarding method comparison studies. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Refutational Text and Multiple External Representations as a Method to Remediate the Misinterpretation of Box Plots

ERIC Educational Resources Information Center

Lem, Stephanie; Baert, Kathy; Ceulemans, Eva; Onghena, Patrick; Verschaffel, Lieven; Van Dooren, Wim

2017-01-01

The ability to interpret graphs is highly important in modern society, but has proven to be a challenge for many people. In this paper, two teaching methods were used to remediate one specific misinterpretation: the area misinterpretation of box plots. First, we used refutational text to explicitly state and invalidate the area misinterpretation…

Measuring water and sediment discharge from a road plot with a settling basin and tipping bucket

Treesearch

Thomas A. Black; Charles H. Luce

2013-01-01

A simple empirical method quantifies water and sediment production from a forest road surface, and is well suited for calibration and validation of road sediment models. To apply this quantitative method, the hydrologic technician installs bordered plots on existing typical road segments and measures coarse sediment production in a settling tank. When a tipping bucket...

Measuring temperature-dependent activation energy in thermally activated processes: a 2D Arrhenius plot method.

PubMed

Li, Jian V; Johnston, Steven W; Yan, Yanfa; Levi, Dean H

2010-03-01

Thermally activated processes are characterized by two key quantities, activation energy (E(a)) and pre-exponential factor (nu(0)), which may be temperature dependent. The accurate measurement of E(a), nu(0), and their temperature dependence is critical for understanding the thermal activation mechanisms of non-Arrhenius processes. However, the classic 1D Arrhenius plot-based methods cannot unambiguously measure E(a), nu(0), and their temperature dependence due to the mathematical impossibility of resolving two unknown 1D arrays from one 1D experimental data array. Here, we propose a 2D Arrhenius plot method to solve this fundamental problem. Our approach measures E(a) at any temperature from matching the first and second moments of the data calculated with respect to temperature and rate in the 2D temperature-rate plane, and therefore is able to unambiguously solve E(a), nu(0), and their temperature dependence. The case study of deep level emission in a Cu(In,Ga)Se(2) solar cell using the 2D Arrhenius plot method reveals clear temperature dependent behavior of E(a) and nu(0), which has not been observable by its 1D predecessors.

Non-parametric and least squares Langley plot methods

NASA Astrophysics Data System (ADS)

Kiedron, P. W.; Michalsky, J. J.

2016-01-01

Langley plots are used to calibrate sun radiometers primarily for the measurement of the aerosol component of the atmosphere that attenuates (scatters and absorbs) incoming direct solar radiation. In principle, the calibration of a sun radiometer is a straightforward application of the Bouguer-Lambert-Beer law V = V0e-τ ṡ m, where a plot of ln(V) voltage vs. m air mass yields a straight line with intercept ln(V0). This ln(V0) subsequently can be used to solve for τ for any measurement of V and calculation of m. This calibration works well on some high mountain sites, but the application of the Langley plot calibration technique is more complicated at other, more interesting, locales. This paper is concerned with ferreting out calibrations at difficult sites and examining and comparing a number of conventional and non-conventional methods for obtaining successful Langley plots. The 11 techniques discussed indicate that both least squares and various non-parametric techniques produce satisfactory calibrations with no significant differences among them when the time series of ln(V0)'s are smoothed and interpolated with median and mean moving window filters.

Impact of surface wettability on S-layer recrystallization: a real-time characterization by QCM-D

PubMed Central

Vianna, Ana C; Moreno-Cencerrado, Alberto; Pum, Dietmar; Sleytr, Uwe B

2017-01-01

Quartz crystal microbalance with dissipation monitoring (QCM-D) has been employed to study the assembly and recrystallization kinetics of isolated SbpA bacterial surface proteins onto silicon dioxide substrates of different surface wettability. Surface modification by UV/ozone oxidation or by vapor deposition of 1H,1H,2H,2H-perfluorododecyltrichlorosilane yielded hydrophilic or hydrophobic samples, respectively. Time evolution of frequency and dissipation factors, either individually or combined as the so-called Df plots, showed a much faster formation of crystalline coatings for hydrophobic samples, characterized by a phase-transition peak at around the 70% of the total mass adsorbed. This behavior has been proven to mimic, both in terms of kinetics and film assembly steps, the recrystallization taking place on an underlying secondary cell-wall polymer (SCWP) as found in bacteria. Complementary atomic force microscopy (AFM) experiments corroborate these findings and reveal the impact on the final structure achieved. PMID:28144568

The degradation of the antitumor agent gemcitabine hydrochloride in an acidic aqueous solution at pH 3.2 and identification of degradation products.

PubMed

Jansen, P J; Akers, M J; Amos, R M; Baertschi, S W; Cooke, G G; Dorman, D E; Kemp, C A; Maple, S R; McCune, K A

2000-07-01

A study of the degradation kinetics of gemcitabine hydrochloride (2'-deoxy-2',2'-difluorocytidine) in aqueous solution at pH 3.2 was conducted. The degradation of gemcitabine followed pseudo first-order kinetics, and rate constants were determined at four different temperatures. These rates were used to construct an Arrhenius plot from which degradation rates at lower temperatures were extrapolated and activation energy calculated. Four major degradation products were identified. Only one of these degradation products, the uridine analogue of gemcitabine, was a known degradation product of gemcitabine and was identified by comparison with synthesized material. The other three degradation products were isolated and characterized by spectroscopic techniques. Two of these products were determined to be the diastereomeric 6-hydroxy-5, 6-dihydro-2'-deoxy-2',2'-difluorouridines, and the other product was determined to be O(6),5'-cyclo-5,6-dihydro-2'-deoxy-2', 2'-difluorouridine. The mechanisms of formation of these degradation products are discussed.

Oxidation Kinetics of a NiPtTi High Temperature Shape Memory Alloy

NASA Technical Reports Server (NTRS)

Smialek, James L.; Humphrey, Donald L.; Noebe, Ronald D.

2007-01-01

A high temperature shape memory alloy (HTSMA), Ni30Pt50Ti, with an M(sub s) near 600 C, was isothermally oxidized in air for 100 hr over the temperature range of 500 to 900 C. Parabolic kinetics were confirmed by log-log and parabolic plots and showed no indication of fast transient oxidation. The overall behavior could be best described by the Arrhenius relationship: k(sub p) = 1.64 x 10(exp 12)[(-250 kJ/mole)/RT] mg(sup 2)/cm(sup 4)hr. This is about a factor of 4 reduction compared to values measured here for a binary Ni47Ti commercial SMA. The activation energy agreed with most literature values for TiO2 scale growth measured for elemental Ti and other NiTi alloys. Assuming uniform alloy depletion of a 20 mil (0.5 mm) dia. HTSMA wire, approx. 1 percent Ti reduction is predicted after 20,000 hr oxidation at 500 C, but becomes much more serious at higher temperatures.

PET brain kinetics studies of 11C-ITMM and 11C-ITDM,radioprobes for metabotropic glutamate receptor type 1, in a nonhuman primate

PubMed Central

Yamasaki, Tomoteru; Maeda, Jun; Fujinaga, Masayuki; Nagai, Yuji; Hatori, Akiko; Yui, Joji; Xie, Lin; Nengaki, Nobuki; Zhang, Ming-Rong

2014-01-01

The metabotropic glutamate receptor type 1 (mGluR1) is a novel target protein for the development of new drugs against central nervous system disorders. Recently, we have developed 11C-labeled PET probes 11C-ITMM and 11C-ITDM, which demonstrate similar profiles, for imaging of mGluR1. In the present study, we compared 11C-ITMM and 11C-ITDM PET imaging and quantitative analysis in the monkey brain. Respective PET images showed similar distribution of uptake in the cerebellum, thalamus, and cingulate cortex. Slightly higher uptake was detected with 11C-ITDM than with 11C-ITMM. For the kinetic analysis using the two-tissue compartment model (2-TCM), the distribution volume (VT) in the cerebellum, an mGluR1-rich region in the brain, was 2.5 mL∙cm-3 for 11C-ITMM and 3.6 mL∙cm-3 for 11C-ITDM. By contrast, the VT in the pons, a region with negligible mGluR1 expression, was similarly low for both radiopharmaceuticals. Based on these results, we performed noninvasive PET quantitative analysis with general reference tissue models using the time-activity curve of the pons as a reference region. We confirmed the relationship and differences between the reference tissue models and 2-TCM using correlational scatter plots and Bland-Altman plots analyses. Although the scattergrams of both radiopharmaceuticals showed over- or underestimations of reference tissue model-based the binding potentials against 2-TCM, there were no significant differences between the two kinetic analysis models. In conclusion, we first demonstrated the potentials of 11C-ITMM and 11C-ITDM for noninvasive PET quantitative analysis using reference tissue models. In addition, our findings suggest that 11C-ITDM may be superior to 11C-ITMM as a PET probe for imaging of mGluR1, because regional VT values in PET with 11C-ITDM were higher than those of 11C-ITMM. Clinical studies of 11C-ITDM in humans will be necessary in the future. PMID:24795840

PET brain kinetics studies of (11)C-ITMM and (11)C-ITDM,radioprobes for metabotropic glutamate receptor type 1, in a nonhuman primate.

PubMed

Yamasaki, Tomoteru; Maeda, Jun; Fujinaga, Masayuki; Nagai, Yuji; Hatori, Akiko; Yui, Joji; Xie, Lin; Nengaki, Nobuki; Zhang, Ming-Rong

2014-01-01

The metabotropic glutamate receptor type 1 (mGluR1) is a novel target protein for the development of new drugs against central nervous system disorders. Recently, we have developed (11)C-labeled PET probes (11)C-ITMM and (11)C-ITDM, which demonstrate similar profiles, for imaging of mGluR1. In the present study, we compared (11)C-ITMM and (11)C-ITDM PET imaging and quantitative analysis in the monkey brain. Respective PET images showed similar distribution of uptake in the cerebellum, thalamus, and cingulate cortex. Slightly higher uptake was detected with (11)C-ITDM than with (11)C-ITMM. For the kinetic analysis using the two-tissue compartment model (2-TCM), the distribution volume (VT) in the cerebellum, an mGluR1-rich region in the brain, was 2.5 mL∙cm(-3) for (11)C-ITMM and 3.6 mL∙cm(-3) for (11)C-ITDM. By contrast, the VT in the pons, a region with negligible mGluR1 expression, was similarly low for both radiopharmaceuticals. Based on these results, we performed noninvasive PET quantitative analysis with general reference tissue models using the time-activity curve of the pons as a reference region. We confirmed the relationship and differences between the reference tissue models and 2-TCM using correlational scatter plots and Bland-Altman plots analyses. Although the scattergrams of both radiopharmaceuticals showed over- or underestimations of reference tissue model-based the binding potentials against 2-TCM, there were no significant differences between the two kinetic analysis models. In conclusion, we first demonstrated the potentials of (11)C-ITMM and (11)C-ITDM for noninvasive PET quantitative analysis using reference tissue models. In addition, our findings suggest that (11)C-ITDM may be superior to (11)C-ITMM as a PET probe for imaging of mGluR1, because regional VT values in PET with (11)C-ITDM were higher than those of (11)C-ITMM. Clinical studies of (11)C-ITDM in humans will be necessary in the future.

The albatross plot: A novel graphical tool for presenting results of diversely reported studies in a systematic review.

PubMed

Harrison, Sean; Jones, Hayley E; Martin, Richard M; Lewis, Sarah J; Higgins, Julian P T

2017-09-01

Meta-analyses combine the results of multiple studies of a common question. Approaches based on effect size estimates from each study are generally regarded as the most informative. However, these methods can only be used if comparable effect sizes can be computed from each study, and this may not be the case due to variation in how the studies were done or limitations in how their results were reported. Other methods, such as vote counting, are then used to summarize the results of these studies, but most of these methods are limited in that they do not provide any indication of the magnitude of effect. We propose a novel plot, the albatross plot, which requires only a 1-sided P value and a total sample size from each study (or equivalently a 2-sided P value, direction of effect and total sample size). The plot allows an approximate examination of underlying effect sizes and the potential to identify sources of heterogeneity across studies. This is achieved by drawing contours showing the range of effect sizes that might lead to each P value for given sample sizes, under simple study designs. We provide examples of albatross plots using data from previous meta-analyses, allowing for comparison of results, and an example from when a meta-analysis was not possible. Copyright © 2017 The Authors. Research Synthesis Methods Published by John Wiley & Sons Ltd.

Partitioning evapotranspiration fluxes with water stable isotopic measurements: from the lab to the field

NASA Astrophysics Data System (ADS)

Quade, M. E.; Brueggemann, N.; Graf, A.; Rothfuss, Y.

2017-12-01

Water stable isotopes are powerful tools for partitioning net into raw water fluxes such as evapotranspiration (ET) into soil evaporation (E) and plant transpiration (T). The isotopic methodology for ET partitioning is based on the fact that E and T have distinct water stable isotopic compositions, which in turn relies on the fact that each flux is differently affected by isotopic kinetic effects. An important work to be performed in parallel to field measurements is to better characterize these kinetic effects in the laboratory under controlled conditions. A soil evaporation laboratory experiment was conducted to retrieve characteristic values of the kinetic fractionation factor (αK) under varying soil and atmospheric water conditions. For this we used a combined soil and atmosphere column to monitor the soil and atmospheric water isotopic composition profiles at a high temporal and vertical resolution in a nondestructive manner by combining micro-porous membranes and laser spectroscopy. αK was calculated by using a well-known isotopic evaporation model in an inverse mode with the isotopic composition of E as one input variable, which was determined using a micro-Keeling regression plot. Knowledge on αK was further used in the field (Selhausen, North Rhine-Westphalia, Germany) to partition ET of catch crops and sugar beet (Beta vulgaris) during one growing season. Soil and atmospheric water isotopic profiles were measured automatically across depths and heights following a similar modus operandi as in the laboratory experiment. Additionally, a newly developed continuously moving elevator was used to obtain water vapor isotopic composition profiles with a high vertical resolution between soil surface, plant canopy and atmosphere. Finally, soil and plant samples were collected destructively to provide a comparison with the traditional isotopic methods. Our results illustrate the changing proportions of T and E along the growing season and demonstrate the applicability of our new non-destructive approach to field conditions.

Evaluation of columns packed with shell particles with compounds of pharmaceutical interest.

PubMed

Ruta, Joséphine; Zurlino, Daria; Grivel, Candice; Heinisch, Sabine; Veuthey, Jean-Luc; Guillarme, Davy

2012-03-09

The commercial C18 columns packed with sub-3 μm shell particles were tested and compared to a reference UHPLC column, in terms of kinetic performance as well as selectivity, retention capability, peak shape and loading capacity. For this purpose, a set of pharmaceutically relevant molecules was selected, including acidic, neutral and basic drugs. Regarding kinetic performance, h(opt) values for the shell particles were found between 1.7 and 2, while the UHPLC column provided a value of approximately 2.5. However, this impressive performance should be considered with caution, particularly for the construction of kinetic plots since h(opt) values were sometimes related to the column dimensions, depending on the provider (h(opt) comprised between 1.8 and 2.6 for longer columns of 150 mm packed with shell particles). Despite the non-porous inner core of the shell particles representing between 25 and 36% of the particle, we demonstrated that the decrease in retention was on the maximum equal to 15% for Ascentis column while Acquity and Poroshell were strictly equivalent in terms of retention. Concerning loading capacity, it remains comparable to that of fully porous sub-2 μm particles and always more pronounced with 0.1% formic acid vs. phosphate buffer. The loading capacity of the different columns was found to be better correlated to the pore volume or surface coverage than the shell thickness. Experimentally, the most pronounced overloading was observed with the Poroshell. Finally, the selectivity and peak shape were evaluated using a mixture of basic and acidic drugs. It appears that results were very similar between sub-3 μm shell particles and fully porous sub-2-μm particles for our mixture of compounds, showing the ability to transfer existing methods to shell particles, with only limited adjustments. This study confirms the potential of columns packed with shell particles and demonstrates the interest of such column technology with pharmaceutical compounds. Copyright © 2011 Elsevier B.V. All rights reserved.

Effects of fasting and semistarvation on the kinetics of active and passive sugar absorption across the small intestine in vivo.

PubMed Central

Debnam, E S; Levin, R J

1975-01-01

The effects of dietary restriction on the kinetics of absorption in vivo of glucose, galactose and alpha-methyl glucoside were assessed by electrical and chemical methods in the rat jejunum. 2. The 'apparent Km', maximum absorption or Vmax (mu-mole/10 cm. 15 min) and maximum potential difference (p.d.max) were obtained for the jejunal electrogenic active transfer mechanism from the transfer p.d.s and the chemical absorption data corrected for diffusion using various graphical kinetic plots. 3. Fasting for 3 days greatly decreased the 'apparent Kms', obtained from electrical or chemical data, for all the sugars but had no effect on those for L-valine or L-methionine. Semistarvation caused a less pronounced reduction of the 'apparent Kms' for the sugars. The dietary-induced change in 'apparent Km' for glucose was also observed in the fasted hamster. One interpretation of these changes is that the affinity of the carriers for sugars increases during dietary restriction; the greater the level of restriction the greater the increase. 4. Fasting and semistarvation caused large reductions in the Vmax. These reductions were correlated with a reduced enterocyte population estimated by changes in enterocyte column size. 5. The reduction in the Vmax for galactose was mainly accounted for by the decrease in enterocyte population. In the case of glucose, other factors such as reduced enterocyte metabolism or changes in the carriers must be involved to explain the discrepancy between the large decrease in Vmax and the enterocyte column size. 6. Fasting and semi-starvation had complex, differential actions on the p.d.max for glucose, galactose and alpha-methyl glucoside. These changes did not correlate with those observed in the Vmax measured chemically. 7. A standard diet obtained from two commercial sources was found to differ greatly in its effect on the electrogenic transfer system for alpha-methyl glucoside but had no effect on those for galactose and glucose. PMID:1206572

Volcano plots in analyzing differential expressions with mRNA microarrays.

PubMed

Li, Wentian

2012-12-01

A volcano plot displays unstandardized signal (e.g. log-fold-change) against noise-adjusted/standardized signal (e.g. t-statistic or -log(10)(p-value) from the t-test). We review the basic and interactive use of the volcano plot and its crucial role in understanding the regularized t-statistic. The joint filtering gene selection criterion based on regularized statistics has a curved discriminant line in the volcano plot, as compared to the two perpendicular lines for the "double filtering" criterion. This review attempts to provide a unifying framework for discussions on alternative measures of differential expression, improved methods for estimating variance, and visual display of a microarray analysis result. We also discuss the possibility of applying volcano plots to other fields beyond microarray.

Method of Continuous Variations: Applications of Job Plots to the Study of Molecular Associations in Organometallic Chemistry[**

PubMed Central

Renny, Joseph S.; Tomasevich, Laura L.; Tallmadge, Evan H.; Collum, David B.

2014-01-01

Applications of the method of continuous variations—MCV or the Method of Job—to problems of interest to organometallic chemists are described. MCV provides qualitative and quantitative insights into the stoichiometries underlying association of m molecules of A and n molecules of B to form AmBn. Applications to complex ensembles probe associations that form metal clusters and aggregates. Job plots in which reaction rates are monitored provide relative stoichiometries in rate-limiting transition structures. In a specialized variant, ligand- or solvent-dependent reaction rates are dissected into contributions in both the ground states and transition states, which affords insights into the full reaction coordinate from a single Job plot. Gaps in the literature are identified and critiqued. PMID:24166797

Combustor kinetic energy efficiency analysis of the hypersonic research engine data

NASA Astrophysics Data System (ADS)

Hoose, K. V.

1993-11-01

A one-dimensional method for measuring combustor performance is needed to facilitate design and development scramjet engines. A one-dimensional kinetic energy efficiency method is used for measuring inlet and nozzle performance. The objective of this investigation was to assess the use of kinetic energy efficiency as an indicator for scramjet combustor performance. A combustor kinetic energy efficiency analysis was performed on the Hypersonic Research Engine (HRE) data. The HRE data was chosen for this analysis due to its thorough documentation and availability. The combustor, inlet, and nozzle kinetic energy efficiency values were utilized to determine an overall engine kinetic energy efficiency. Finally, a kinetic energy effectiveness method was developed to eliminate thermochemical losses from the combustion of fuel and air. All calculated values exhibit consistency over the flight speed range. Effects from fuel injection, altitude, angle of attack, subsonic-supersonic combustion transition, and inlet spike position are shown and discussed. The results of analyzing the HRE data indicate that the kinetic energy efficiency method is effective as a measure of scramjet combustor performance.

Radiobiological Optimization of Combination Radiopharmaceutical Therapy Applied to Myeloablative Treatment of Non-Hodgkin’s Lymphoma

PubMed Central

Hobbs, Robert F; Wahl, Richard L; Frey, Eric C; Kasamon, Yvette; Song, Hong; Huang, Peng; Jones, Richard J; Sgouros, George

2014-01-01

Combination treatment is a hallmark of cancer therapy. Although the rationale for combination radiopharmaceutical therapy was described in the mid ‘90s, such treatment strategies have only been implemented clinically recently, and without a rigorous methodology for treatment optimization. Radiobiological and quantitative imaging-based dosimetry tools are now available that enable rational implementation of combined targeted radiopharmaceutical therapy. Optimal implementation should simultaneously account for radiobiological normal organ tolerance while optimizing the ratio of two different radiopharmaceuticals required to maximize tumor control. We have developed such a methodology and applied it to hypothetical myeloablative treatment of non-hodgkin’s lymphoma (NHL) patients using 131I-tositumomab and 90Y-ibritumomab tiuxetan. Methods The range of potential administered activities (AA) is limited by the normal organ maximum tolerated biologic effective doses (MTBEDs) arising from the combined radiopharmaceuticals. Dose limiting normal organs are expected to be the lungs for 131I-tositumomab and the liver for 90Y-ibritumomab tiuxetan in myeloablative NHL treatment regimens. By plotting the limiting normal organ constraints as a function of the AAs and calculating tumor biological effective dose (BED) along the normal organ MTBED limits, the optimal combination of activities is obtained. The model was tested using previously acquired patient normal organ and tumor kinetic data and MTBED values taken from the literature. Results The average AA values based solely on normal organ constraints was (19.0 ± 8.2) GBq with a range of 3.9 – 36.9 GBq for 131I-tositumomab, and (2.77 ± 1.64) GBq with a range of 0.42 – 7.54 GBq for 90Y-ibritumomab tiuxetan. Tumor BED optimization results were calculated and plotted as a function of AA for 5 different cases, established using patient normal organ kinetics for the two radiopharmaceuticals. Results included AA ranges which would deliver 95 % of the maximum tumor BED, which allows for informed inclusion of clinical considerations, such as a maximum allowable 131I administration. Conclusions A rational approach for combination radiopharmaceutical treatment has been developed within the framework of a proven 3-dimensional personalized dosimetry software, 3D-RD, and applied to the myeloablative treatment of NHL. We anticipate combined radioisotope therapy will ultimately supplant single radioisotope therapy, much as combination chemotherapy has substantially replaced single agent chemotherapy. PMID:23918734

Evaluation of a short dynamic 18F-fluoride PET/CT scanning method to assess bone metabolic activity in spinal orthopedics.

PubMed

Peters, Marloes J M; Wierts, Roel; Jutten, Elisabeth M C; Halders, Servé G E A; Willems, Paul C P H; Brans, Boudewijn

2015-11-01

A complication after spinal fusion surgery is pseudarthrosis, but its radiological diagnosis is of limited value. (18)F-fluoride PET with its ability to assess bone metabolism activity could be of value. The goal of this study was to assess the clinical feasibility of calculating the static standardized uptake value (SUV) from a short dynamic scan without the use of blood sampling, thereby obtaining all dynamic and static parameters in a scan of only 30 min. This approach was tested on a retrospective patient population with persisting pain after spinal fusion surgery. In 16 patients, SUVs (SUV max, SUV mean) and kinetic parameters (K 1, k 2, k 3, v b, K i,NLR, K 1/k 2, k 3/(k 2 + k 3), K i,patlak) were derived from static and dynamic PET/CT scans of operated and control regions of the spine, after intravenous administration of 156-214 MBq (18)F-fluoride. Parameter differences between control and operated regions, as well as between pseudarthrosis and fused segments were evaluated. SUVmean at 30 and 60 min was calculated from kinetic parameters obtained from the dynamic data set (SUV mean,2TCM). Agreement between measured and calculated SUVs was evaluated through Bland-Altman plots. Overall, statistically significant differences between control and operated regions were observed for SUV max, SUV mean, K i,NLR, K i,patlak, K 1/k 2 and k 3/(k 2 + k 3). Diagnostic CT showed pseudarthrosis in 6/16 patients, while in 10/16 patients, segments were fused. Of all parameters, only those regarding the incorporation of bone [K i,NLR, K i,patlak, k 3/(k 2 + k 3)] differed statistically significant in the intervertebral disc space between the pseudarthrosis and fused patients group. The mean values of the patient-specific blood clearance rate [Formula: see text] differed statistically significant between the pseudarthrosis and the fusion group, with a p value of 0.011. This may correspond with the lack of statistical significance of the SUV values between pseudarthrosis and fused patients. Bland-Altman plots show that calculated SUV mean,2TCM values corresponded well with the measured SUV mean values. This study shows the feasibility of a 30-min dynamic (18)F-fluoride PET/CT scanning and this may provide dynamic parameters clinically relevant to the diagnosis of pseudarthrosis.

Automated Transition State Theory Calculations for High-Throughput Kinetics.

PubMed

Bhoorasingh, Pierre L; Slakman, Belinda L; Seyedzadeh Khanshan, Fariba; Cain, Jason Y; West, Richard H

2017-09-21

A scarcity of known chemical kinetic parameters leads to the use of many reaction rate estimates, which are not always sufficiently accurate, in the construction of detailed kinetic models. To reduce the reliance on these estimates and improve the accuracy of predictive kinetic models, we have developed a high-throughput, fully automated, reaction rate calculation method, AutoTST. The algorithm integrates automated saddle-point geometry search methods and a canonical transition state theory kinetics calculator. The automatically calculated reaction rates compare favorably to existing estimated rates. Comparison against high level theoretical calculations show the new automated method performs better than rate estimates when the estimate is made by a poor analogy. The method will improve by accounting for internal rotor contributions and by improving methods to determine molecular symmetry.

[Effect of comprehensive control and prevention for chronic disease in demonstration plot of Chongqing].

PubMed

Qi, Li; Ding, Xian-bin; Mao, De-qiang; Feng, Lian-gui; Wang, Yu-lin; Jiao, Yan; Zhang, Chun-hua; Lü, Xiao-yan; Li, Hong; Xia, Yi-yin

2013-03-01

To evaluate the effect of comprehensive control and prevention for chronic diseases in demonstration plot of Chongqing. Residents were enrolled through multi-stage stratified random sampling method from 17 districts or counties which had successfully established demonstration plots and 21 districts or counties which had not established demonstration plots (non-demonstration plot for short) yet on May, 2012. Questionnaire was designed to survey awareness of health knowledge, health behaviors and utilization of health supportive tools. The results were analyzed by SPSS 15.0 software. We investigated 15 108 residents, 6156 of which were in demonstration plot and others (8951) were not. The findings revealed the percentage of the people who were aware the national action of health lifestyle in demonstration plot and in non-demonstration plot were 44.4% (2734/6157) and 40.2% (3598/8951), respectively, and the awareness of the hypertension risk of too much sodium were 72.4% (4458/6156) and 67.5% (6042/8951), respectively, and the awareness of the cardinal vascular disease (CVD) risk of obesity and overweight were 77.2% (4753/6157) and 69.6% (6230/8951), respectively. About the residents' health behaviors in demonstration plot and in non-demonstration plot, the utilization rates of salt restriction scoop or pot were 23.5% (1447/6157) and 17.9% (1602/8951), and the utilization rates of oil restriction pot were 16.7% (1028/6157) and 11.8% (1064/8951), respectively. Totally, 33 of the 37 indexes were shown higher in demonstration plot than that in non-demonstration plot (P < 0.05). The chronic diseases comprehensive control and prevention in demonstration plot was more effective, and the remarkable improvement of health knowledge and behaviors level had been achieved in demonstration plot.

Dynamical density delay maps: simple, new method for visualising the behaviour of complex systems

PubMed Central

2014-01-01

Background Physiologic signals, such as cardiac interbeat intervals, exhibit complex fluctuations. However, capturing important dynamical properties, including nonstationarities may not be feasible from conventional time series graphical representations. Methods We introduce a simple-to-implement visualisation method, termed dynamical density delay mapping (“D3-Map” technique) that provides an animated representation of a system’s dynamics. The method is based on a generalization of conventional two-dimensional (2D) Poincaré plots, which are scatter plots where each data point, x(n), in a time series is plotted against the adjacent one, x(n + 1). First, we divide the original time series, x(n) (n = 1,…, N), into a sequence of segments (windows). Next, for each segment, a three-dimensional (3D) Poincaré surface plot of x(n), x(n + 1), h[x(n),x(n + 1)] is generated, in which the third dimension, h, represents the relative frequency of occurrence of each (x(n),x(n + 1)) point. This 3D Poincaré surface is then chromatised by mapping the relative frequency h values onto a colour scheme. We also generate a colourised 2D contour plot from each time series segment using the same colourmap scheme as for the 3D Poincaré surface. Finally, the original time series graph, the colourised 3D Poincaré surface plot, and its projection as a colourised 2D contour map for each segment, are animated to create the full “D3-Map.” Results We first exemplify the D3-Map method using the cardiac interbeat interval time series from a healthy subject during sleeping hours. The animations uncover complex dynamical changes, such as transitions between states, and the relative amount of time the system spends in each state. We also illustrate the utility of the method in detecting hidden temporal patterns in the heart rate dynamics of a patient with atrial fibrillation. The videos, as well as the source code, are made publicly available. Conclusions Animations based on density delay maps provide a new way of visualising dynamical properties of complex systems not apparent in time series graphs or standard Poincaré plot representations. Trainees in a variety of fields may find the animations useful as illustrations of fundamental but challenging concepts, such as nonstationarity and multistability. For investigators, the method may facilitate data exploration. PMID:24438439

Adsorption of leather dyes on activated carbon from leather shaving wastes: kinetics, equilibrium and thermodynamics studies.

PubMed

Manera, Christian; Tonello, Andrezza Piroli; Perondi, Daniele; Godinho, Marcelo

2018-03-23

In this work, the adsorption of Acid Black 210 (AB210) and Acid Red 357 (AR357) onto activated carbon prepared from leather shaving wastes (ACLW) was investigated. The activated carbon presented a surface area of 800.4 m²/g with an average pore size of 1.27 nm. The kinetic study showed that the adsorption of both dyes followed the Elovich kinetic model while the AB210 and AR357 isotherm data were well described by the Langmuir and BET models, respectively. Furthermore, the Boyd plot revealed that the adsorption of the leather dyes on activated carbon was mainly governed by film diffusion. The pH had a strong influence on the adsorption, and the higher amounts of dye adsorbed were obtained at pH 2. The obtained activated carbon exhibited a high monolayer adsorption capacity of 573.9 and 204.4 mg/g for AB210 and AR357, respectively. Its high capacity is mainly attributed to its basicity (0.17 mmol/g) and high surface area. Desorption efficiency of the spent activated carbon was found to be 54.3% and 43.0% for AB210 and AR357, respectively. The spontaneity of the process was demonstrated by the negative values of the Gibbs free energy change.

Reaction kinetics and inhibition of adenosine kinase from Leishmania donovani.

PubMed

Bhaumik, D; Datta, A K

1988-04-01

The reaction kinetics and the inhibitor specificity of adenosine kinase (ATP:adenosine 5'-phosphotransferase, EC 2.7.1.20) from Leishmania donovani, have been analysed using homogeneous preparation of the enzyme. The reaction proceeds with equimolar stoichiometry of each reactant. Double reciprocal plots of initial velocity studies in the absence of products yielded intersecting lines for both adenosine and Mg2+-ATP. AMP is a competitive inhibitor of the enzyme with respect to adenosine and noncompetitive inhibitor with respect to ATP. In contrast, ADP was a noncompetitive inhibitor with respect to both adenosine and ATP, with inhibition by ADP becoming uncompetitive at very high concentration of ATP. Parallel equilibrium dialysis experiments against [3H]adenosine and [gamma-32P]ATP resulted in binding of adenosine to fre enzyme. Tubercidin (7-deazaadenosine) and 6-methyl-mercaptopurine riboside acted as substrates for the enzyme and were found to inhibit adenosine phosphorylation competitively in vitro. 'Substrate efficiency (Vmax/Km)' and 'turnover numbers (Kcat)' of the enzyme with respect to specific analogs were determined. Taken together the results suggest that (a) the kinetic mechanism of adenosine kinase is sequential Bi-Bi, (b) AMP and ADP may regulate enzyme activity in vivo and (c) tubercidin and 6-methylmercaptopurine riboside are monophosphorylated by the parasite enzyme.

Comparative kinetic analysis on thermal degradation of some cephalosporins using TG and DSC data

PubMed Central

2013-01-01

Background The thermal decomposition of cephalexine, cefadroxil and cefoperazone under non-isothermal conditions using the TG, respectively DSC methods, was studied. In case of TG, a hyphenated technique, including EGA, was used. Results The kinetic analysis was performed using the TG and DSC data in air for the first step of cephalosporin’s decomposition at four heating rates. The both TG and DSC data were processed according to an appropriate strategy to the following kinetic methods: Kissinger-Akahira-Sunose, Friedman, and NPK, in order to obtain realistic kinetic parameters, even if the decomposition process is a complex one. The EGA data offer some valuable indications about a possible decomposition mechanism. The obtained data indicate a rather good agreement between the activation energy’s values obtained by different methods, whereas the EGA data and the chemical structures give a possible explanation of the observed differences on the thermal stability. A complete kinetic analysis needs a data processing strategy using two or more methods, but the kinetic methods must also be applied to the different types of experimental data (TG and DSC). Conclusion The simultaneous use of DSC and TG data for the kinetic analysis coupled with evolved gas analysis (EGA) provided us a more complete picture of the degradation of the three cephalosporins. It was possible to estimate kinetic parameters by using three different kinetic methods and this allowed us to compare the Ea values obtained from different experimental data, TG and DSC. The thermodegradation being a complex process, the both differential and integral methods based on the single step hypothesis are inadequate for obtaining believable kinetic parameters. Only the modified NPK method allowed an objective separation of the temperature, respective conversion influence on the reaction rate and in the same time to ascertain the existence of two simultaneous steps. PMID:23594763

Application of the new Cross Recurrence Plots to multivariate data

NASA Astrophysics Data System (ADS)

Thiel, M.; Romano, C.; Kurths, J.

2003-04-01

We extend and then apply the method of the new Cross Recurrence Plots (XRPs) to multivariate data. After introducing the new method we carry out an analysis of spatiotemporal ecological data. We compute not only the Rényi entropies and cross entropies by XRP, that allow to draw conclusions about the coupling of the systems, but also find a prediction horizon for intermediate time scales.

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

Houtz, Robert, L.

This project focused on a molecular and biochemical characterization of the protein methyltransferases responsible for methylation of the LS and SS in Rubisco, and the associated functional consequences accompanying these modifications. Our results provided some of the most informative structural and mechanistic understandings of SET domain protein methyltransferases. These results also positioned us to provide the first unambiguous assignment of the kinetic reaction mechanism for SET-domain protein methyltransferases, and to design and engineer an alternative substrate for Rubisco LSMT, enabling substrate specificity and functional significance studies. We demonstrated that the minimal substrate recognized by Rubisco LSMT is free lysine asmore » well as monomethyllysine, an observation corroborated both by structural analyses as well as enzymatic activity and subsequent product distribution analyses. Ternary complexes between Rubisco LSMT and free lysine compared to complexes with monomethyllysine demonstrated that the structural basis for multiple methyl group additions is a consequence of hydrogen-bond driven spatial shifts in the amino group of Lys-14, which maintains the direct in-line geometry necessary for SN2 nucleophilic attack. The structural observations are also consistent with the previous proposal that the multiplicity of methyl group additions takes place through a processive mechanism, with successive methyl group additions to an enzyme protein complex which does not disassociate prior to the formation of trimethyllysine. This mechanism has important implications, since the regulation of gene expression by SET domain histone methyltransferases is not only dependent on site-specific lysine methylation, but also the degree of methylation. We examined the kinetic reaction mechanism for three different types of SET domain protein methyltransferases, each under conditions supporting mono-, di-, or trimethyllysine formation corroborated by product analyses. Additionally, the tight initial binding of Rubisco LSMT to Rubisco also allowed us to design a novel immobilized complex between Rubisco and Rubisco LSMT, which allowed for an unambiguous demonstration of the requirement for trimethyllysine formation prior to disassociation of the Rubisco LSMT:Rubisco complex, and therefore proof of the processive mechanism for methyl group transfer. These kinetic studies also demonstrated that an important factor has been overlooked in all kinetic analyses of SET domain protein methyltransferases reported to date. This factor is the influence of the low turnover number for SET domain protein methyltransferases and how, relative to the time-frame of kinetic enzyme assays, this can generate changes in kinetic profiles shifting reciprocal plot patterns from random/ordered bi-bi to the real kinetic reaction mechanism plots of ping-pong. Although the ternary complexes of Rubisco LSMT with S-Adenosylhomocysteine and lysine and monomethyllysine were informative in regard to reaction mechanism, they were not helpful in identifying the mechanism used by Rubisco LSMT for determining substrate specificity. We were unsuccessful at obtaining ternary complexes of Rubisco LSMT with bound synthetic polypeptide substrates, as has been reported for several histone methyltransferases. However, we were able to model a polypeptide sequence corresponding to the N-terminal region of the LS of Rubisco into the apparent substrate binding cleft in Rubisco LSMT. Knowledge of the determinants of polypeptide substrate specificity are important for identifying possible alternate substrates, as well as the possibility of generating more desirable substrates amenable to site-directed mutagenesis experiments unlike Rubisco. We determined that Rubisco LSMT is capable of methylating synthetic polypeptide mimics of the N-terminal region of the LS, both free as well as conjugated to keyhole limpet hemacyanin, but with considerable less efficiency than intact holoenzyme.« less

Impacts of sampling design and estimation methods on nutrient leaching of intensively monitored forest plots in the Netherlands.

PubMed

de Vries, W; Wieggers, H J J; Brus, D J

2010-08-05

Element fluxes through forest ecosystems are generally based on measurements of concentrations in soil solution at regular time intervals at plot locations sampled in a regular grid. Here we present spatially averaged annual element leaching fluxes in three Dutch forest monitoring plots using a new sampling strategy in which both sampling locations and sampling times are selected by probability sampling. Locations were selected by stratified random sampling with compact geographical blocks of equal surface area as strata. In each sampling round, six composite soil solution samples were collected, consisting of five aliquots, one per stratum. The plot-mean concentration was estimated by linear regression, so that the bias due to one or more strata being not represented in the composite samples is eliminated. The sampling times were selected in such a way that the cumulative precipitation surplus of the time interval between two consecutive sampling times was constant, using an estimated precipitation surplus averaged over the past 30 years. The spatially averaged annual leaching flux was estimated by using the modeled daily water flux as an ancillary variable. An important advantage of the new method is that the uncertainty in the estimated annual leaching fluxes due to spatial and temporal variation and resulting sampling errors can be quantified. Results of this new method were compared with the reference approach in which daily leaching fluxes were calculated by multiplying daily interpolated element concentrations with daily water fluxes and then aggregated to a year. Results show that the annual fluxes calculated with the reference method for the period 2003-2005, including all plots, elements and depths, lies only in 53% of the cases within the range of the average +/-2 times the standard error of the new method. Despite the differences in results, both methods indicate comparable N retention and strong Al mobilization in all plots, with Al leaching being nearly equal to the leaching of SO(4) and NO(3) with fluxes expressed in mol(c) ha(-1) yr(-1). This illustrates that Al release, which is the clearest signal of soil acidification, is mainly due to the external input of SO(4) and NO(3).

Substrate and pH-Dependent Kinetic Profile of 3-Mercaptopropionate Dioxygenase from Pseudomonas aeruginosa.

PubMed

Fellner, Matthias; Aloi, Sekotilani; Tchesnokov, Egor P; Wilbanks, Sigurd M; Jameson, Guy N L

2016-03-08

Thiol dioxygenases catalyze the synthesis of sulfinic acids in a range of organisms from bacteria to mammals. A thiol dioxygenase from the bacterium Pseudomonas aeruginosa oxidizes both 3-mercaptopropionic acid and cysteine, with a ∼70 fold preference for 3-mercaptopropionic acid over all pHs. This substrate reactivity is widened compared to other thiol dioxygenases and was exploited in this investigation of the residues important for activity. A simple model incorporating two protonation events was used to fit profiles of the Michaelis-Menten parameters determined at different pH values for both substrates. The pKs determined using plots of k(cat)/Km differ at low pH, but not in a way easily attributable to protonation of the substrate alone and share a common value at higher pH. Plots of k(cat) versus pH are also quite different at low pH showing the monoprotonated ES complexes with 3-mercaptopropionic acid and cysteine have different pKs. At higher pH, k(cat) decreases sigmoidally with a similar pK regardless of substrate. Loss of reactivity at high pH is attributed to deprotonation of tyrosine 159 and its influence on dioxygen binding. A mechanism is proposed by which deprotonation of tyrosine 159 both blocks oxygen binding and concomitantly promotes cystine formation. Finally, the role of tyrosine 159 was further probed by production of a G95C variant that is able to form a cysteine-tyrosine crosslink homologous to that found in mammalian cysteine dioxygenases. Activity of this variant is severely impaired. Crystallography shows that when un-crosslinked, the cysteine thiol excludes tyrosine 159 from its native position, while kinetic analysis shows that the thioether bond impairs reactivity of the crosslinked form.

Complexity in pH-Dependent Ribozyme Kinetics: Dark pKa Shifts and Wavy Rate-pH Profiles.

PubMed

Frankel, Erica A; Bevilacqua, Philip C

2018-02-06

Charged bases occur in RNA enzymes, or ribozymes, where they play key roles in catalysis. Cationic bases donate protons and perform electrostatic catalysis, while anionic bases accept protons. We previously published simulations of rate-pH profiles for ribozymes in terms of species plots for the general acid and general base that have been useful for understanding how ribozymes respond to pH. In that study, we did not consider interaction between the general acid and general base or interaction with other species on the RNA. Since that report, diverse small ribozyme classes have been discovered, many of which have charged nucleobases or metal ions in the active site that can either directly interact and participate in catalysis or indirectly interact as "influencers". Herein, we simulate experimental rate-pH profiles in terms of species plots in which reverse protonated charged nucleobases interact. These analyses uncover two surprising features of pH-dependent enzyme kinetics. (1) Cooperativity between the general acid and general base enhances population of the functional forms of a ribozyme and manifests itself as hidden or "dark" pK a shifts, real pK a shifts that accelerate the reaction but are not readily observed by standard experimental approaches, and (2) influencers favorably shift the pK a s of proton-transferring nucleobases and manifest themselves as "wavy" rate-pH profiles. We identify parallels with the protein enzyme literature, including reverse protonation and wavelike behavior, while pointing out that RNA is more prone to reverse protonation. The complexities uncovered, which arise from simple pairwise interactions, should aid deconvolution of complex rate-pH profiles for RNA and protein enzymes and suggest veiled catalytic devices for promoting catalysis that can be tested by experiment and calculation.

Comparative study of new shell-type, sub-2 micron fully porous and monolith stationary phases, focusing on mass-transfer resistance.

PubMed

Oláh, Erzsébet; Fekete, Szabolcs; Fekete, Jeno; Ganzler, Katalin

2010-06-04

Today sub-2 microm packed columns are very popular to conduct fast chromatographic separations. The mass-transfer resistance depends on the particle size but some practical limits exist not to reach the theoretically expected plate height and mass-transfer resistance. Another approach applies particles with shortened diffusion path to enhance the efficiency of separations. In this study a systematical evaluation of the possibilities of the separations obtained with 5 cm long narrow bore columns packed with new 2.6 microm shell particles (1.9 microm nonporous core surrounded by a 0.35 microm porous shell, Kinetex, Core-Shell), packed with other shell-type particles (Ascentis Express, Fused-Core), totally porous sub-2 microm particles and a 5 cm long narrow bore monolith column is presented. The different commercially available columns were compared by using van Deemter, Knox and kinetic plots. Theoretical Poppe plots were constructed for each column to compare their kinetic performance. Data are presented on polar neutral real-life analytes. Comparison of a low molecular weight compounds (MW=270-430) and a high molecular weight one (MW approximately 900) was conducted. This study proves that the Kinetex column packed with 2.6 microm shell particles is worthy of rivaling to sub-2 microm columns and other commercially available shell-type packings (Ascentis Express or Halo), both for small and large molecule separation. The Kinetex column offers a very flat C term. Utilizing this feature, high flow rates can be applied to accomplish very fast separations without significant loss in efficiency. Copyright 2010 Elsevier B.V. All rights reserved.

Microbial L-phenylalanine ammonia-lyase. Purification, subunit structure and kinetic properties of the enzyme from Rhizoctonia solani.

PubMed Central

Kalghatgi, K K; Subba Rao, P V

1975-01-01

1. Phenylalanine ammonia-lyase (EC 4.3.1.5) was purified to homogeneity from the acetone-dried powders of the mycelial felts of the plant pathogenic fungus Rhizoctonia solani. 2. A useful modification in protamine sulphate treatment to get substantial purification of the enzyme in a single-step is described. 3. The purified enzyme shows bisubstrate activity towards L-phenylalanine and L-tyrosine. 4. It is sensitive to carbonyl reagents and the inhibition is not reversed by gel filtration. 5. The molecular weight of the enzyme as determined by Sephadex G-200 chromatography and sucrose-density-gradient centrifugation is around 330000. 6. The enzyme is made up of two pairs of unidentical subunits, with a molecular weight of 70000 (alpha) and 90000 (beta) respectively. 7. Studies on initial velocity versus substrate concentration have shown significant deviations from Michaelis-Menten kinetics. 8. The double-reciprocal plots are biphasic (concave downwards) and Hofstee plots show a curvilinear pattern. 9. The apparent Km value increases from 0.18 mM to as high as 5.0 mM with the increase in the concentration of the substrate and during this process the Vmax, increases by 2-2.5-fold. 10. The value of Hill coefficient is 0.5. 11. Steady-state rates of phenylalanine ammonia-lyase reaction in the presence of inhibitors like D-phenylalanine, cinnamic, p-coumaric, caffeic, dihydrocaffeic and phenylpyruvic acid have shown that only one molecule of each type of inhibitor binds to a molecule of the enzyme. These observations suggest the involvement of negative homotropic interactions in phenylalanine ammonia-lyase. 12. The enzyme could not be desensitized by treatment with HgCl2, p-chloromercuribenzoic acid or by repeated freezing and thawing. PMID:1191266

An eco-friendly direct spectrofluorimetric method for the determination of irreversible tyrosine kinase inhibitors, neratinib and pelitinib: application to stability studies.

PubMed

Maher, H M; Alzoman, N Z; Shehata, S M

2017-03-01

A new rapid and simple stability-indicating spectrofluorimetric method has been developed for the determination of two irreversible tyrosine kinase inhibitors (TKIs), neratinib (NER) and pelitinib (PEL). The method is based upon measurement of the native fluorescence intensity of both drugs at λ ex 270 nm in aqueous borate buffer solutions (pH 10.5). The fluorescence intensity recorded at 545 nm (NER) and 465 nm (PEL) were rectilinear over the concentration range of 0.1-10 μg/mL for both drugs with a high correlation coefficient (r > 0.999). The proposed method provided low limits of detection and of quantitation of 0.07, 0.11 μg/mL (NER) and 0.02, 0.05 μg/mL (PEL), respectively. The method was successfully applied for the determination of NER and PEL in bulk powder. The proposed methods were fully validated as per the International Conference on Harmonisation (ICH) guidelines. The application of the method was extended to stability studies of both NER and PEL under different forced-degradation conditions (acidic-induced, base-induced, oxidative, wet heat, and photolytic degradation). Moreover, the kinetics of the base-induced and oxidative degradation of both drugs was investigated and the pseudo-first-order rate constants and half-lives were estimated at different temperatures. Also, an Arrhenius plot was applied to predict the stability behaviour of the two drugs at room temperature. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Reducing Modeling Error of Graphical Methods for Estimating Volume of Distribution Measurements in PIB-PET study

PubMed Central

Guo, Hongbin; Renaut, Rosemary A; Chen, Kewei; Reiman, Eric M

2010-01-01

Graphical analysis methods are widely used in positron emission tomography quantification because of their simplicity and model independence. But they may, particularly for reversible kinetics, lead to bias in the estimated parameters. The source of the bias is commonly attributed to noise in the data. Assuming a two-tissue compartmental model, we investigate the bias that originates from modeling error. This bias is an intrinsic property of the simplified linear models used for limited scan durations, and it is exaggerated by random noise and numerical quadrature error. Conditions are derived under which Logan's graphical method either over- or under-estimates the distribution volume in the noise-free case. The bias caused by modeling error is quantified analytically. The presented analysis shows that the bias of graphical methods is inversely proportional to the dissociation rate. Furthermore, visual examination of the linearity of the Logan plot is not sufficient for guaranteeing that equilibrium has been reached. A new model which retains the elegant properties of graphical analysis methods is presented, along with a numerical algorithm for its solution. We perform simulations with the fibrillar amyloid β radioligand [11C] benzothiazole-aniline using published data from the University of Pittsburgh and Rotterdam groups. The results show that the proposed method significantly reduces the bias due to modeling error. Moreover, the results for data acquired over a 70 minutes scan duration are at least as good as those obtained using existing methods for data acquired over a 90 minutes scan duration. PMID:20493196

Kinetic hydrogen isotope effects in the concerted mechanism for the hydrolysis of acetals, ketals, and ortho esters

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

Eliason, R.; Kreevoy, M.M.

1978-10-25

The hydrolysis of many ortho esters, and some acetals and ketals, is general acid catalyzed, and in some examples these generate linear Bronsted plots over substantial ranges of catalyst acidity. This suggests that the reaction coordinate is primarily a reorganization of heavy atoms since proton transfer from one oxygen to another has been shown to generate strongly curved Bronsted plots. However, the isotopic fractionation factor for the catalytically active proton in these transition states is substantially less than 1.0; in several examples it is less than 0.5. Such values have been thought to require that the reaction coordinate be largelymore » a motion of the hydrogen giving the low fractionation factor. This dilemma has been resolved by the observation and rationalization of fractionation factors as low as 0.28 for stable, hydrogen bridge-bonded complexes, AHA/sup -/. A similar, bounded coordinate is now suggested for the catalytically active protons in question. This permits the reaction coordinate to be pictured. 3 figures, 2 tables.« less

Estrogen Transport in Surface Runoff from Agricultural Fields Treated with Two Application Methods of Dairy Manure.

PubMed

Mina, Odette; Gall, Heather E; Saporito, Louis S; Kleinman, Peter J A

2016-11-01

This study compares two methods of dairy manure application-surface broadcast and shallow disk injection-on the fate and transport of natural estrogens in surface runoff from 12 field plots in central Pennsylvania. Ten natural surface runoff events were sampled over a 9-mo period after fall manure application. Results show that the range of estrogen concentrations observed in surface runoff from the broadcast plots was several orders of magnitude higher (>5000 ng L) than the concentrations in runoff from the shallow disk injection plots (<10 ng L). Additionally, the transport dynamics differed, with the majority of the estrogen loads from the surface broadcast plots occurring during the first rainfall event after application, whereas the majority of the loads from the shallow disk injection plots occurred more than 6 mo later during a hail storm event. Total estrogen loads were, on average, two orders of magnitude lower for shallow disk injection compared with surface broadcast. Independent of the method of manure application, 17α-estradiol and estrone were preserved in the field for as long as 9 mo after application. Overall, injection of manure shows promise in reducing the potential for off-site losses of hormones from manure-amended soils. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

The albatross plot: A novel graphical tool for presenting results of diversely reported studies in a systematic review

PubMed Central

Jones, Hayley E.; Martin, Richard M.; Lewis, Sarah J.; Higgins, Julian P.T.

2017-01-01

Abstract Meta‐analyses combine the results of multiple studies of a common question. Approaches based on effect size estimates from each study are generally regarded as the most informative. However, these methods can only be used if comparable effect sizes can be computed from each study, and this may not be the case due to variation in how the studies were done or limitations in how their results were reported. Other methods, such as vote counting, are then used to summarize the results of these studies, but most of these methods are limited in that they do not provide any indication of the magnitude of effect. We propose a novel plot, the albatross plot, which requires only a 1‐sided P value and a total sample size from each study (or equivalently a 2‐sided P value, direction of effect and total sample size). The plot allows an approximate examination of underlying effect sizes and the potential to identify sources of heterogeneity across studies. This is achieved by drawing contours showing the range of effect sizes that might lead to each P value for given sample sizes, under simple study designs. We provide examples of albatross plots using data from previous meta‐analyses, allowing for comparison of results, and an example from when a meta‐analysis was not possible. PMID:28453179

Nonideal isentropic gas flow through converging-diverging nozzles

NASA Technical Reports Server (NTRS)

Bober, W.; Chow, W. L.

1990-01-01

A method for treating nonideal gas flows through converging-diverging nozzles is described. The method incorporates the Redlich-Kwong equation of state. The Runge-Kutta method is used to obtain a solution. Numerical results were obtained for methane gas. Typical plots of pressure, temperature, and area ratios as functions of Mach number are given. From the plots, it can be seen that there exists a range of reservoir conditions that require the gas to be treated as nonideal if an accurate solution is to be obtained.

Alpha – omega and omega – alpha phase transformations in zirconium under hydrostatic pressure: A 3D mesoscale study

DOE PAGES

Yeddu, Hemantha Kumar; Zong, Hongxiang; Lookman, Turab

2015-09-28

Here, a three dimensional (3D) elastoplastic phase-field model is developed for modeling the hydrostatic pressure-induced alpha – omega phase transformation and the reverse phase transformation, i.e. omega – alpha, in zirconium (Zr). Plastic deformation and strain hardening of the material are also considered in the model. The microstructure evolution during both phase transformations is studied. The transformation start pressures at different temperatures are predicted and are plotted as a phase diagram. The effect of phase transformations on the mechanical properties of the material is also studied. The input data corresponding to pure Zr are acquired from experimental studies as wellmore » as by using the CALPHAD method. Our simulations show that three different omega variants form as laths. On release of pressure, reverse phase transformation initiates at lath boundaries. We observe that both phase transformations are martensitic in nature and also occur at the same pressure, i.e. little hysteresis. The transformation start pressures and the kinetics of the transformation predicted by our model are in good agreement with experimental results.« less

Novel RuCoSe as non-platinum catalysts for oxygen reduction reaction in microbial fuel cells

NASA Astrophysics Data System (ADS)

Rozenfeld, Shmuel; Schechter, Michal; Teller, Hanan; Cahan, Rivka; Schechter, Alex

2017-09-01

Microbial electrochemical cells (MECs) are explored for the conversion of acetate directly to electrical energy. This device utilizes a Geobacter sulfurreducens anode and a novel RuCoSe air cathode. RuCoSe synthesized in selected compositions by a borohydride reduction method produces amorphous structures of powdered agglomerates. Oxygen reduction reaction (ORR) was measured in a phosphate buffer solution pH 7 using a rotating disc electrode (RDE), from which the kinetic current (ik) was measured as a function of potential and composition. The results show that ik of RuxCoySe catalysts increases in the range of XRu = 0.25 > x > 0.7 and y < 0.15 for all tested potentials. A poisoning study of RuCoSe and Pt catalysts in a high concentration acetate solution shows improved tolerance of RuCoSe to this fuel at acetate concentration ≥500 mM. MEC discharge plots under physiological conditions show that ∼ RuCo2Se (sample S3) has a peak power density of 750 mW cm-2 which is comparable with Pt 900 mW cm-2.

Alpha – omega and omega – alpha phase transformations in zirconium under hydrostatic pressure: A 3D mesoscale study

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

Yeddu, Hemantha Kumar; Zong, Hongxiang; Lookman, Turab

Here, a three dimensional (3D) elastoplastic phase-field model is developed for modeling the hydrostatic pressure-induced alpha – omega phase transformation and the reverse phase transformation, i.e. omega – alpha, in zirconium (Zr). Plastic deformation and strain hardening of the material are also considered in the model. The microstructure evolution during both phase transformations is studied. The transformation start pressures at different temperatures are predicted and are plotted as a phase diagram. The effect of phase transformations on the mechanical properties of the material is also studied. The input data corresponding to pure Zr are acquired from experimental studies as wellmore » as by using the CALPHAD method. Our simulations show that three different omega variants form as laths. On release of pressure, reverse phase transformation initiates at lath boundaries. We observe that both phase transformations are martensitic in nature and also occur at the same pressure, i.e. little hysteresis. The transformation start pressures and the kinetics of the transformation predicted by our model are in good agreement with experimental results.« less

Implementation and Testing of Turbulence Models for the F18-HARV Simulation

NASA Technical Reports Server (NTRS)

Yeager, Jessie C.

1998-01-01

This report presents three methods of implementing the Dryden power spectral density model for atmospheric turbulence. Included are the equations which define the three methods and computer source code written in Advanced Continuous Simulation Language to implement the equations. Time-history plots and sample statistics of simulated turbulence results from executing the code in a test program are also presented. Power spectral densities were computed for sample sequences of turbulence and are plotted for comparison with the Dryden spectra. The three model implementations were installed in a nonlinear six-degree-of-freedom simulation of the High Alpha Research Vehicle airplane. Aircraft simulation responses to turbulence generated with the three implementations are presented as plots.

Automatic Extraction of Small Spatial Plots from Geo-Registered UAS Imagery

NASA Astrophysics Data System (ADS)

Cherkauer, Keith; Hearst, Anthony

2015-04-01

Accurate extraction of spatial plots from high-resolution imagery acquired by Unmanned Aircraft Systems (UAS), is a prerequisite for accurate assessment of experimental plots in many geoscience fields. If the imagery is correctly geo-registered, then it may be possible to accurately extract plots from the imagery based on their map coordinates. To test this approach, a UAS was used to acquire visual imagery of 5 ha of soybean fields containing 6.0 m2 plots in a complex planting scheme. Sixteen artificial targets were setup in the fields before flights and different spatial configurations of 0 to 6 targets were used as Ground Control Points (GCPs) for geo-registration, resulting in a total of 175 geo-registered image mosaics with a broad range of geo-registration accuracies. Geo-registration accuracy was quantified based on the horizontal Root Mean Squared Error (RMSE) of targets used as checkpoints. Twenty test plots were extracted from the geo-registered imagery. Plot extraction accuracy was quantified based on the percentage of the desired plot area that was extracted. It was found that using 4 GCPs along the perimeter of the field minimized the horizontal RMSE and enabled a plot extraction accuracy of at least 70%, with a mean plot extraction accuracy of 92%. The methods developed are suitable for work in many fields where replicates across time and space are necessary to quantify variability.

Discussion of the Investigation Method on the Reaction Kinetics of Metallurgical Reaction Engineering

NASA Astrophysics Data System (ADS)

Du, Ruiling; Wu, Keng; Zhang, Jiazhi; Zhao, Yong

Reaction kinetics of metallurgical physical chemistry which was successfully applied in metallurgy (as ferrous metallurgy, non-ferrous metallurgy) became an important theoretical foundation for subject system of traditional metallurgy. Not only the research methods were very perfect, but also the independent structures and systems of it had been formed. One of the important tasks of metallurgical reaction engineering was the simulation of metallurgical process. And then, the mechanism of reaction process and the conversion time points of different control links should be obtained accurately. Therefore, the research methods and results of reaction kinetics in metallurgical physical chemistry were not very suitable for metallurgical reaction engineering. In order to provide the definite conditions of transmission, reaction kinetics parameters and the conversion time points of different control links for solving the transmission and reaction equations in metallurgical reaction engineering, a new method for researching kinetics mechanisms in metallurgical reaction engineering was proposed, which was named stepwise attempt method. Then the comparison of results between the two methods and the further development of stepwise attempt method were discussed in this paper. As a new research method for reaction kinetics in metallurgical reaction engineering, stepwise attempt method could not only satisfy the development of metallurgical reaction engineering, but also provide necessary guarantees for establishing its independent subject system.

Determination of variability in leaf biomass densities of conifers and mixed conifers under different environmental conditions in the San Joaquin Valley air basin. Final report

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

Temple, P.J.; Mutters, R.J.; Adams, C.

1995-06-01

Biomass sampling plots were established at 29 locations within the dominant vegetation zones of the study area. Estimates of foliar biomass were made for each plot by three independent methods: regression analysis on the basis of tree diameter, calculation of the amount of light intercepted by the leaf canopy, and extrapolation from branch leaf area. Multivariate regression analysis was used to relate these foliar biomass estimates for oak plots and conifer plots to several independent predictor variables, including elevation, slope, aspect, temperature, precipitation, and soil chemical characteristics.

Electrical Arc Ignition Testing of Spacesuit Materials

NASA Technical Reports Server (NTRS)

Smith, Sarah; Gallus, Tim; Tapia, Susana; Ball, Elizabeth; Beeson, Harold

2006-01-01

A viewgraph presentation on electrical arc ignition testing of spacesuit materials is shown. The topics include: 1) Background; 2) Test Objectives; 3) Test Sample Materials; 4) Test Methods; 5) Scratch Test Objectives; 6) Cotton Scratch Test Video; 7) Scratch Test Results; 8) Entire Date Plot; 9) Closeup Data Plot; 10) Scratch Test Problems; 11) Poke Test Objectives; 12) Poke Test Results; 13) Poke Test Problems; 14) Wire-break Test Objectives; 15) Cotton Wire-Break Test Video; 16) High Speed Cotton Wire-break Test Video; 17) Typical Data Plot; 18) Closeup Data Plot; 19) Wire-break Test Results; 20) Wire-break Tests vs. Scratch Tests; 21) Urethane-coated Nylon; and 22) Moleskin.

A gas-kinetic BGK scheme for the compressible Navier-Stokes equations

NASA Technical Reports Server (NTRS)

Xu, Kun

2000-01-01

This paper presents an improved gas-kinetic scheme based on the Bhatnagar-Gross-Krook (BGK) model for the compressible Navier-Stokes equations. The current method extends the previous gas-kinetic Navier-Stokes solver developed by Xu and Prendergast by implementing a general nonequilibrium state to represent the gas distribution function at the beginning of each time step. As a result, the requirement in the previous scheme, such as the particle collision time being less than the time step for the validity of the BGK Navier-Stokes solution, is removed. Therefore, the applicable regime of the current method is much enlarged and the Navier-Stokes solution can be obtained accurately regardless of the ratio between the collision time and the time step. The gas-kinetic Navier-Stokes solver developed by Chou and Baganoff is the limiting case of the current method, and it is valid only under such a limiting condition. Also, in this paper, the appropriate implementation of boundary condition for the kinetic scheme, different kinetic limiting cases, and the Prandtl number fix are presented. The connection among artificial dissipative central schemes, Godunov-type schemes, and the gas-kinetic BGK method is discussed. Many numerical tests are included to validate the current method.

CPdock: the complementarity plot for docking of proteins: implementing multi-dielectric continuum electrostatics.

PubMed

Basu, Sankar

2017-12-07

The complementarity plot (CP) is an established validation tool for protein structures, applicable to both globular proteins (folding) as well as protein-protein complexes (binding). It computes the shape and electrostatic complementarities (S m , E m ) for amino acid side-chains buried within the protein interior or interface and plots them in a two-dimensional plot having knowledge-based probabilistic quality estimates for the residues as well as for the whole structure. The current report essentially presents an upgraded version of the plot with the implementation of the advanced multi-dielectric functionality (as in Delphi version 6.2 or higher) in the computation of electrostatic complementarity to make the validation tool physico-chemically more realistic. The two methods (single- and multi-dielectric) agree decently in their resultant E m values, and hence, provisions for both methods have been kept in the software suite. So to speak, the global electrostatic balance within a well-folded protein and/or a well-packed interface seems only marginally perturbed by the choice of different internal dielectric values. However, both from theoretical as well as practical grounds, the more advanced multi-dielectric version of the plot is certainly recommended for potentially producing more reliable results. The report also presents a new methodology and a variant plot, namely CP dock , based on the same principles of complementarity specifically designed to be used in the docking of proteins. The efficacy of the method to discriminate between good and bad docked protein complexes has been tested on a recent state-of-the-art docking benchmark. The results unambiguously indicate that CP dock can indeed be effective in the initial screening phase of a docking scoring pipeline before going into more sophisticated and computationally expensive scoring functions. CP dock has been made available at https://github.com/nemo8130/CPdock . Graphical Abstract An example showing the efficacy of CP dock to be used in the initial screening phase of a protein-protein docking scoring pipeline.

Evaluation of the Soil Conservation Service curve number methodology using data from agricultural plots

NASA Astrophysics Data System (ADS)

Lal, Mohan; Mishra, S. K.; Pandey, Ashish; Pandey, R. P.; Meena, P. K.; Chaudhary, Anubhav; Jha, Ranjit Kumar; Shreevastava, Ajit Kumar; Kumar, Yogendra

2017-01-01

The Soil Conservation Service curve number (SCS-CN) method, also known as the Natural Resources Conservation Service curve number (NRCS-CN) method, is popular for computing the volume of direct surface runoff for a given rainfall event. The performance of the SCS-CN method, based on large rainfall (P) and runoff (Q) datasets of United States watersheds, is evaluated using a large dataset of natural storm events from 27 agricultural plots in India. On the whole, the CN estimates from the National Engineering Handbook (chapter 4) tables do not match those derived from the observed P and Q datasets. As a result, the runoff prediction using former CNs was poor for the data of 22 (out of 24) plots. However, the match was little better for higher CN values, consistent with the general notion that the existing SCS-CN method performs better for high rainfall-runoff (high CN) events. Infiltration capacity (fc) was the main explanatory variable for runoff (or CN) production in study plots as it exhibited the expected inverse relationship between CN and fc. The plot-data optimization yielded initial abstraction coefficient (λ) values from 0 to 0.659 for the ordered dataset and 0 to 0.208 for the natural dataset (with 0 as the most frequent value). Mean and median λ values were, respectively, 0.030 and 0 for the natural rainfall-runoff dataset and 0.108 and 0 for the ordered rainfall-runoff dataset. Runoff estimation was very sensitive to λ and it improved consistently as λ changed from 0.2 to 0.03.

An alternative representation of the receptance: The 'elliptical plane' and its modal properties

NASA Astrophysics Data System (ADS)

Montalvão, Diogo; Amafabia, Daerefa-a. Mitsheal

2018-03-01

Modal Identification from Frequency Response Functions (FRFs) has been extensively investigated up to the point its research reached a stagnation state. Yet, a new approach to determine the modal damping factors from FRFs was recently proposed, showing that there still is scope for new findings in the field. Contrary to other modal identification methods which are based on the dynamic motion governing equations, the method used the dissipated energy per cycle of vibration as a starting point. For lightly damped systems with conveniently spaced modes, it produced quite accurate results, especially when compared to the well-known method of the inverse. The method used a plot of the sine of the phase of the receptance against its amplitude, whereby damping was determined from the slope of a linear fit to the resulting plot. In this paper, it is shown that this plot has other (perhaps more important) special properties that were not explored before. Near resonant frequencies, its shape is elliptical, whereby the real and imaginary parts of the modal constants can be determined from numerical curve-fitting. This finding allowed developing a new method which formulation is presented in this paper. The method is discussed through numerical and experimental examples. Although the intention is not to present a new modal identification method that is superior to other existing ones (like the method of the inverse or those based on the Nyquist plot), the authors believe that this new representation of the receptance and its properties may bring valuable insights for other researchers in the field.

Purification of 6-phosphogluconate dehydrogenase from parsley (Petroselinum hortense) leaves and investigation of some kinetic properties.

PubMed

Demir, Hülya; Ciftçi, Mehmet; Küfrevioğlu, O Irfan

2003-02-01

In this study, 6-phosphogluconate dehydrogenase (E.C.1.1.44; 6PGD) was purified from parsley (Petroselinum hortense) leaves, and analysis of the kinetic behavior and some properties of the enzyme were investigated. The purification consisted of three steps that are preparation of homogenate ammonium sulfate fractionation and on DEAE-Sephadex A50 ion exchange. The enzyme was obtained with a yield of 49% and had a specific activity of 18.3 U (mg proteins)(-1) (Lehninger, A.L.; Nelson, D.L.; Cox, M.M. Principles of Biochemistry, 2nd Ed.; Worth Publishers Inc.: N.Y., 2000, 558-560). The overall purification was about 339-fold. A temperature of +4 degrees C was maintained during the purification process. Enzyme activity was spectrophotometrically measured according to the Beutler method at 340 mn. In order to control the purification of the enzyme, SDS-polyacrylamide gel electrophoresis was carried out in 4% and 10% acrylamide for stacking and running gel, respectively. SDS-polyacrylamide gel electrophoresis showed a single band for enzyme. The molecular weight was found to be 97.5 kDa by Sephadex G-150 gel filtration chromatography. A protein band corresponding to a subunit molecular weight of 24.1 kDa was obtained on SDS-polyacrylamide gel electrophoresis. For the enzymes, the stable pH, optimum pH, and optimum temperature were found as 8.0, 8.0, and 50 degrees C, respectively. In addition, KM and Vmax values for NADP+ and G6-P at optimum pH and 25 degrees C were determined by means of Lineweaver-Burk plots.

Kinetic mechanism of ATP-sulphurylase from rat chondrosarcoma.

PubMed Central

Lyle, S; Geller, D H; Ng, K; Westley, J; Schwartz, N B

1994-01-01

ATP-sulphurylase catalyses the production of adenosine 5'-phosphosulphate (APS) from ATP and free sulphate with the release of PPi. APS kinase phosphorylates the APS intermediate to produce adenosine 3'-phosphate 5'-phosphosulphate (PAPS). The kinetic mechanism of rat chondrosarcoma ATP-sulphurylase was investigated by steady-state methods in the physiologically forward direction as well as the reverse direction. The sulphurylase activity was coupled to APS kinase activity in order to overcome the thermodynamic constraints of the sulphurylase reaction in the forward direction. Double-reciprocal initial-velocity plots for the forward sulphurylase intersect to the left of the ordinate for this reaction. KmATP and Kmsulphate were found to be 200 and 97 microM respectively. Chlorate, a competitive inhibitor with respect to sulphate, showed uncompetitive inhibition with respect to ATP with an apparent Ki of 1.97 mM. Steady-state data from experiments in the physiologically reverse direction also yielded double-reciprocal initial-velocity patterns that intersect to the left of the ordinate axis, with a KmAPS of 39 microM and a Kmpyrophosphate of 18 microM. The results of steady-state experiments in which Mg2+ was varied indicated that the true substrate is the MgPPi complex. An analogue of APS, adenosine 5'-[beta-methylene]phosphosulphate, was a linear inhibitor competitive with APS and non-competitive with respect to MgPPi. The simplest formal mechanism that agrees with all the data is an ordered steady-state single displacement with MgATP as the leading substrate in the forward direction and APS as the leading substrate in the reverse direction. PMID:8042976

Investigation into the Use of Normal and Half-Normal Plots for Interpreting Results from Screening Experiments.

DTIC Science & Technology

1987-03-25

by Lloyd (1952) using generalized least squares instead of ordinary least squares, and by Wilk, % 20 Gnanadesikan , and Freeny (1963) using a maximum...plot. The half-normal distribution is a special case of the gamma distribution proposed by Wilk, Gnanadesikan , and Huyett (1962). VARIATIONS ON THE... Gnanadesikan , R. Probability plotting methods for the analysis of data. Biometrika, 1968, 55, 1-17. This paper describes and discusses graphical techniques

Simpson's paradox visualized: The example of the Rosiglitazone meta-analysis

PubMed Central

Rücker, Gerta; Schumacher, Martin

2008-01-01

Background Simpson's paradox is sometimes referred to in the areas of epidemiology and clinical research. It can also be found in meta-analysis of randomized clinical trials. However, though readers are able to recalculate examples from hypothetical as well as real data, they may have problems to easily figure where it emerges from. Method First, two kinds of plots are proposed to illustrate the phenomenon graphically, a scatter plot and a line graph. Subsequently, these can be overlaid, resulting in a overlay plot. The plots are applied to the recent large meta-analysis of adverse effects of rosiglitazone on myocardial infarction and to an example from the literature. A large set of meta-analyses is screened for further examples. Results As noted earlier by others, occurrence of Simpson's paradox in the meta-analytic setting, if present, is associated with imbalance of treatment arm size. This is well illustrated by the proposed plots. The rosiglitazone meta-analysis shows an effect reversion if all trials are pooled. In a sample of 157 meta-analyses, nine showed an effect reversion after pooling, though non-significant in all cases. Conclusion The plots give insight on how the imbalance of trial arm size works as a confounder, thus producing Simpson's paradox. Readers can see why meta-analytic methods must be used and what is wrong with simple pooling. PMID:18513392

An evaluation of rapid methods for monitoring vegetation characteristics of wetland bird habitat

USGS Publications Warehouse

Tavernia, Brian G.; Lyons, James E.; Loges, Brian W.; Wilson, Andrew; Collazo, Jaime A.; Runge, Michael C.

2016-01-01

Wetland managers benefit from monitoring data of sufficient precision and accuracy to assess wildlife habitat conditions and to evaluate and learn from past management decisions. For large-scale monitoring programs focused on waterbirds (waterfowl, wading birds, secretive marsh birds, and shorebirds), precision and accuracy of habitat measurements must be balanced with fiscal and logistic constraints. We evaluated a set of protocols for rapid, visual estimates of key waterbird habitat characteristics made from the wetland perimeter against estimates from (1) plots sampled within wetlands, and (2) cover maps made from aerial photographs. Estimated percent cover of annuals and perennials using a perimeter-based protocol fell within 10 percent of plot-based estimates, and percent cover estimates for seven vegetation height classes were within 20 % of plot-based estimates. Perimeter-based estimates of total emergent vegetation cover did not differ significantly from cover map estimates. Post-hoc analyses revealed evidence for observer effects in estimates of annual and perennial covers and vegetation height. Median time required to complete perimeter-based methods was less than 7 percent of the time needed for intensive plot-based methods. Our results show that rapid, perimeter-based assessments, which increase sample size and efficiency, provide vegetation estimates comparable to more intensive methods.

Quantification of the vertical translocation rate of soil solid-phase material by the magnetic tracer method

NASA Astrophysics Data System (ADS)

Zhidkin, A. P.; Gennadiev, A. N.

2016-07-01

Approaches to the quantification of the vertical translocation rate of soil solid-phase material by the magnetic tracer method have been developed; the tracer penetration depth and rate have been determined, as well as the radial distribution of the tracer in chernozems (Chernozems) and dark gray forest soils (Luvisols) of Belgorod oblast under natural steppe and forest vegetation and in arable lands under agricultural use of different durations. It has been found that the penetration depth of spherical magnetic particles (SMPs) during their 150-year-occurrence in soils of a forest plot is 68 cm under forest, 58 cm on a 100-year old plowland, and only 49 cm on a 150-year-old plowland. In the chernozems of the steppe plot, the penetration depth of SMPs exceeds the studied depth of 70 cm both under natural vegetation and on the plowlands. The penetration rates of SMPs deep into the soil vary significantly among the key plots: 0.92-1.32 mm/year on the forest plot and 1.47-1.63 mm/year on the steppe plot, probably because of the more active recent turbation activity of soil animals.

A new method for estimating the demographic history from DNA sequences: an importance sampling approach

PubMed Central

Ait Kaci Azzou, Sadoune; Larribe, Fabrice; Froda, Sorana

2015-01-01

The effective population size over time (demographic history) can be retraced from a sample of contemporary DNA sequences. In this paper, we propose a novel methodology based on importance sampling (IS) for exploring such demographic histories. Our starting point is the generalized skyline plot with the main difference being that our procedure, skywis plot, uses a large number of genealogies. The information provided by these genealogies is combined according to the IS weights. Thus, we compute a weighted average of the effective population sizes on specific time intervals (epochs), where the genealogies that agree more with the data are given more weight. We illustrate by a simulation study that the skywis plot correctly reconstructs the recent demographic history under the scenarios most commonly considered in the literature. In particular, our method can capture a change point in the effective population size, and its overall performance is comparable with the one of the bayesian skyline plot. We also introduce the case of serially sampled sequences and illustrate that it is possible to improve the performance of the skywis plot in the case of an exponential expansion of the effective population size. PMID:26300910

The isometric log-ratio (ilr)-ion plot: A proposed alternative to the Piper diagram

USGS Publications Warehouse

Shelton, Jenna L.; Engle, Mark A.; Buccianti, Antonella; Blondes, Madalyn S.

2018-01-01

The Piper diagram has been a staple for the analysis of water chemistry data since its introduction in 1944. It was conceived to be a method for water classification, determination of potential water mixing between end-members, and to aid in the identification of chemical reactions controlling a sample set. This study uses the information gleaned over the years since the release of the Piper diagram and proposes an alternative to it, capturing the strengths of the original diagram while adding new ideas to increase its robustness. The new method uses compositional data analysis to create 4 isometric log-ratio coordinates for the 6 major chemical species analyzed in the Piper diagram and transforms the data to a 4-field bi-plot, the ilr-ion plot. This ilr-ion plot conveys all of the information in the Piper diagram (water mixing, water types, and chemical reactions) while also visualizing additional data, the ability to examine Ca2+/Mg2+ versus Cl-/SO42−. The Piper and the ilr-ion plot were also compared using multiple synthetic and real datasets in order to illustrate the caveats and the advantages of using either diagram to analyze water chemistry data. Although there are challenges with using the ilr-ion plot (e.g., missing or zero values zeros in the dataset must be imputed by positive real numbers), it appears that the use of compositional data analysis coupled with the ilr-ion plot provides a more in-depth and complete analysis of water quality data compared to the original Piper diagram.

Using volcano plots and regularized-chi statistics in genetic association studies.

PubMed

Li, Wentian; Freudenberg, Jan; Suh, Young Ju; Yang, Yaning

2014-02-01

Labor intensive experiments are typically required to identify the causal disease variants from a list of disease associated variants in the genome. For designing such experiments, candidate variants are ranked by their strength of genetic association with the disease. However, the two commonly used measures of genetic association, the odds-ratio (OR) and p-value may rank variants in different order. To integrate these two measures into a single analysis, here we transfer the volcano plot methodology from gene expression analysis to genetic association studies. In its original setting, volcano plots are scatter plots of fold-change and t-test statistic (or -log of the p-value), with the latter being more sensitive to sample size. In genetic association studies, the OR and Pearson's chi-square statistic (or equivalently its square root, chi; or the standardized log(OR)) can be analogously used in a volcano plot, allowing for their visual inspection. Moreover, the geometric interpretation of these plots leads to an intuitive method for filtering results by a combination of both OR and chi-square statistic, which we term "regularized-chi". This method selects associated markers by a smooth curve in the volcano plot instead of the right-angled lines which corresponds to independent cutoffs for OR and chi-square statistic. The regularized-chi incorporates relatively more signals from variants with lower minor-allele-frequencies than chi-square test statistic. As rare variants tend to have stronger functional effects, regularized-chi is better suited to the task of prioritization of candidate genes. Copyright © 2013 Elsevier Ltd. All rights reserved.

Rainfall simulators in hydrological and geomorphological sciences: benefits, applications and future research directions

NASA Astrophysics Data System (ADS)

Iserloh, Thomas; Cerdà, Artemi; Fister, Wolfgang; Seitz, Steffen; Keesstra, Saskia; Green, Daniel; Gabriels, Donald

2017-04-01

Rainfall simulators are used extensively within the hydrological and geomorphological sciences and provide a useful investigative tool to understand many processes, such as: (i) plot-scale runoff, infiltration and erosion; (ii) irrigation and crop management, and; (iii) investigations into flooding within a laboratory setting. Although natural rainfall is desirable as it represents actual conditions in a given geographic location, data acquisition relying on natural rainfall is often hindered by its unpredictable nature. Furthermore, rainfall characteristics such as the intensity, duration, drop size distribution and kinetic energy cannot be spatially or temporally regulated or repeated between experimentation. Rainfall simulators provide a suitable method to overcome the issues associated with depending on potentially erratic and unpredictable natural rainfall as they allow: (i) multiple measurements to be taken quickly without waiting for suitable natural rainfall conditions; (ii) the simulation of spatially and/or temporally controlled rainfall patterns over a given plot area, and; (iii) the creation of a closed environment, allowing simplified measurement of input and output conditions. There is no standardisation of rainfall simulation and as such, rainfall simulators differ in their design, rainfall characteristics and research application. Although this impedes drawing meaningful comparisons between studies, this allows researchers to create a bespoke and tailored rainfall simulator for the specific research application. This paper summarises the rainfall simulators used in European research institutions (Universities of Trier, Valencia, Basel, Tuebingen, Wageningen, Loughborough and Ghent) to investigate a number of hydrological and geomorphological issues and includes details on the design specifications (such as the extent and characteristics of simulated rainfall), as well as a discussion of the purpose and application of the rainfall simulator.

Phosphoryl transfer is not rate-limiting for the ROCK I-catalyzed kinase reaction.

PubMed

Futer, Olga; Saadat, Ahmad R; Doran, John D; Raybuck, Scott A; Pazhanisamy, S

2006-06-27

Rho-associated coiled-coil kinase, ROCK, is implicated in Rho-mediated cell adhesion and smooth muscle contraction. Animal models suggest that the inhibition of ROCK can ameliorate conditions, such as vasospasm, hypertension, and inflammation. As part of our effort to design novel inhibitors of ROCK, we investigated the kinetic mechanism of ROCK I. Steady-state bisubstrate kinetics, inhibition kinetics, isotope partition analysis, viscosity effects, and presteady-state kinetics were used to explore the kinetic mechanism. Plots of reciprocals of initial rates obtained in the presence of nonhydrolyzable ATP analogues and the small molecule inhibitor of ROCK, Y-27632, against the reciprocals of the peptide concentrations yielded parallel lines (uncompetitive pattern). This pattern is indicative of an ordered binding mechanism, with the peptide adding first. The staurosporine analogue K252a, however, gave a noncompetitive pattern. When a pulse of (33)P-gamma-ATP mixed with ROCK was chased with excess unlabeled ATP and peptide, 0.66 enzyme equivalent of (33)P-phosphate was incorporated into the product in the first turnover. The presence of ATPase activity coupled with the isotope partition data is a clear evidence for the existence of a viable [E-ATP] complex in the kinase reaction and implicates a random binding mechanism. The k(cat)/K(m) parameters were fully sensitive to viscosity (viscosity effects of 1.4 +/- 0.2 and 0.9 +/- 0.3 for ATP and peptide 5, respectively), and therefore, the barriers to dissociation of either substrate are higher than the barrier for the phosphoryl transfer step. As a consequence, not all the binding steps are at fast equilibrium. The observation of a burst in presteady-state kinetics (k(b) = 10.2 +/- 2.1 s(-)(1)) and the viscosity effect on k(cat) of 1.3 +/- 0.2 characterize the phosphoryl transfer step to be fast and the release of product and/or the enzyme isomerization step accompanying it as rate-limiting at V(max) conditions. From the multiple kinetic studies, most of the rate constants for the individual steps were either evaluated or estimated.

Precipitation of silicon from splat-cooled Al-Si alloys

NASA Technical Reports Server (NTRS)

Matyja, H.; Russell, K. C.; Grant, N. J.; Giessen, B. C.

1975-01-01

Splat cooled Al-Si solid solutions with 1 to 11 at.% Si were prepared and their precipitation kinetics were studied by transmission electron microscopy. The time required for appearance of particles visible at a magnification of 35,000 times was determined at temperatures between 248 K and 573 K. The resulting Arrhenius plots yielded activation energies ranging from 55 to 40 plus or minus 2kJ/mol over the composition range. Precipitate densities were higher and denuded zones of 100 to 150 nm were narrower than in comparable solid quenched samples. The activation energies are explained in terms of excess point defect concentrations.

Double-deprotected chemically amplified photoresists (DD-CAMP): higher-order lithography

NASA Astrophysics Data System (ADS)

Earley, William; Soucie, Deanna; Hosoi, Kenji; Takahashi, Arata; Aoki, Takashi; Cardineau, Brian; Miyauchi, Koichi; Chun, Jay; O'Sullivan, Michael; Brainard, Robert

2017-03-01

The synthesis and lithographic evaluation of 193-nm and EUV photoresists that utilize a higher-order reaction mechanism of deprotection is presented. Unique polymers utilize novel blocking groups that require two acid-catalyzed steps to be removed. When these steps occur with comparable reaction rates, the overall reaction can be higher order (<= 1.85). The LWR of these resists is plotted against PEB time for a variety of compounds to acquire insight into the effectiveness of the proposed higher-order mechanisms. Evidence acquired during testing of these novel photoresist materials supports the conclusion that higher-order reaction kinetics leads to improved LWR vs. control resists.

An exploration of viscosity models in the realm of kinetic theory of liquids originated fluids

NASA Astrophysics Data System (ADS)

Hussain, Azad; Ghafoor, Saadia; Malik, M. Y.; Jamal, Sarmad

The preeminent perspective of this article is to study flow of an Eyring Powell fluid model past a penetrable plate. To find the effects of variable viscosity on fluid model, continuity, momentum and energy equations are elaborated. Here, viscosity is taken as function of temperature. To understand the phenomenon, Reynold and Vogel models of variable viscosity are incorporated. The highly non-linear partial differential equations are transfigured into ordinary differential equations with the help of suitable similarity transformations. The numerical solution of the problem is presented. Graphs are plotted to visualize the behavior of pertinent parameters on the velocity and temperature profiles.

Redefining the utility of the three-isotope method

NASA Astrophysics Data System (ADS)

Cao, Xiaobin; Bao, Huiming

2017-09-01

The equilibrium isotope fractionation factor αeq is a fundamental parameter in the study of stable isotope effects. Experimentally, it has been difficult to establish that a system has attained equilibrium. The three-isotope method, using the initial trajectory of changing isotope ratios (e.g. 16O, 17O, and 18O) to deduce the final equilibrium point of isotope exchange, has long been hailed as the most rigorous experimental approach. However, over the years some researchers have cautioned on the limitations of this method, but the foundation of three-isotope method has not been properly examined and the method is still widely used in calibrating αeq for both traditional and increasingly non-traditional isotope systems today. Here, using water-water and dissolved CO2-water oxygen exchange as model systems, we conduct an isotopologues-specific kinetic analysis of the exchange processes and explore the underlying assumptions and validity of the three-isotope method. We demonstrate that without knowing the detailed exchange kinetics a priori the three-isotope method cannot lead to a reliable αeq. For a two-reservoir exchanging system, α determined by this method may be αeq, kinetic isotope effect, or apparent kinetic isotope effect, which can all bear different values. When multiple reservoirs exist during exchange, the evolving trajectory can be complex and hard to predict. Instead of being a tool for αeq determination, three-isotope method should be used as a tool for studying kinetic isotope effect, apparent kinetic isotope effect, and detailed exchange kinetics in diverse systems.

NASCAP user's manual

NASA Technical Reports Server (NTRS)

Mandell, M. J.; Harvey, J. M.; Katz, I.

1977-01-01

The NASCAP (NASA Charging Analyzer Program) code simulates the charging process for a complex object in either tenuous plasma or ground test environment. Detailed specifications needed to run the code are presented. The object definition section, OBJDEF, allows the test object to be easily defined in the cubic mesh. The test object is composed of conducting sections which may be wholly or partially covered with thin dielectric coatings. The potential section, POTENT, obtains the electrostatic potential in the space surrounding the object. It uses the conjugate gradient method to solve the finite element formulation of Poisson's equation. The CHARGE section of NASCAP treats charge redistribution among the surface cells of the object as well as charging through radiation bombardment. NASCAP has facilities for extensive graphical output, including several types of object display plots, potential contour plots, space charge density contour plots, current density plots, and particle trajectory plots.

Prediction of free turbulent mixing using a turbulent kinetic energy method

NASA Technical Reports Server (NTRS)

Harsha, P. T.

1973-01-01

Free turbulent mixing of two-dimensional and axisymmetric one- and two-stream flows is analyzed by a relatively simple turbulent kinetic energy method. This method incorporates a linear relationship between the turbulent shear and the turbulent kinetic energy and an algebraic relationship for the length scale appearing in the turbulent kinetic energy equation. Good results are obtained for a wide variety of flows. The technique is shown to be especially applicable to flows with heat and mass transfer, for which nonunity Prandtl and Schmidt numbers may be assumed.

Comparative analysis of the folding dynamics and kinetics of an engineered knotted protein and its variants derived from HP0242 of Helicobacter pylori

NASA Astrophysics Data System (ADS)

Wang, Liang-Wei; Liu, Yu-Nan; Lyu, Ping-Chiang; Jackson, Sophie E.; Hsu, Shang-Te Danny

2015-09-01

Understanding the mechanism by which a polypeptide chain thread itself spontaneously to attain a knotted conformation has been a major challenge in the field of protein folding. HP0242 is a homodimeric protein from Helicobacter pylori with intertwined helices to form a unique pseudo-knotted folding topology. A tandem HP0242 repeat has been constructed to become the first engineered trefoil-knotted protein. Its small size renders it a model system for computational analyses to examine its folding and knotting pathways. Here we report a multi-parametric study on the folding stability and kinetics of a library of HP0242 variants, including the trefoil-knotted tandem HP0242 repeat, using far-UV circular dichroism and fluorescence spectroscopy. Equilibrium chemical denaturation of HP0242 variants shows the presence of highly populated dimeric and structurally heterogeneous folding intermediates. Such equilibrium folding intermediates retain significant amount of helical structures except those at the N- and C-terminal regions in the native structure. Stopped-flow fluorescence measurements of HP0242 variants show that spontaneous refolding into knotted structures can be achieved within seconds, which is several orders of magnitude faster than previously observed for other knotted proteins. Nevertheless, the complex chevron plots indicate that HP0242 variants are prone to misfold into kinetic traps, leading to severely rolled-over refolding arms. The experimental observations are in general agreement with the previously reported molecular dynamics simulations. Based on our results, kinetic folding pathways are proposed to qualitatively describe the complex folding processes of HP0242 variants.

How Should Blood Glucose Meter System Analytical Performance Be Assessed?

PubMed

Simmons, David A

2015-08-31

Blood glucose meter system analytical performance is assessed by comparing pairs of meter system and reference instrument blood glucose measurements measured over time and across a broad array of glucose values. Consequently, no single, complete, and ideal parameter can fully describe the difference between meter system and reference results. Instead, a number of assessment tools, both graphical (eg, regression plots, modified Bland-Altman plots, and error grid analysis) and tabular (eg, International Organization for Standardization guidelines, mean absolute difference, and mean absolute relative difference) have been developed to evaluate meter system performance. The strengths and weaknesses of these methods of presenting meter system performance data, including a new method known as Radar Plots, are described here. © 2015 Diabetes Technology Society.

Iron oxide nanoparticle-based magnetic resonance method to monitor release kinetics from polymeric particles with high resolution.

PubMed

Chan, Minnie; Schopf, Eric; Sankaranarayanan, Jagadis; Almutairi, Adah

2012-09-18

A new method to precisely monitor rapid release kinetics from polymeric particles using super paramagnetic iron oxide nanoparticles, specifically by measuring spin-spin relaxation time (T(2)), is reported. Previously, we have published the formulation of logic gate particles from an acid-sensitive poly-β-aminoester ketal-2 polymer. Here, a series of poly-β-aminoester ketal-2 polymers with varying hydrophobicities were synthesized and used to formulate particles. We attempted to measure fluorescence of released Nile red to determine whether the structural adjustments could finely tune the release kinetics in the range of minutes to hours; however, this standard technique did not differentiate each release rate of our series. Thus, a new method based on encapsulation of iron oxide nanoparticles was developed, which enabled us to resolve the release kinetics of our particles. Moreover, the kinetics matched the relative hydrophobicity order determined by octanol-water partition coefficients. To the best of our knowledge, this method provides the highest resolution of release kinetics to date.

Method and apparatus for determining minority carrier diffusion length in semiconductors

DOEpatents

Goldstein, Bernard; Dresner, Joseph; Szostak, Daniel J.

1983-07-12

Method and apparatus are provided for determining the diffusion length of minority carriers in semiconductor material, particularly amorphous silicon which has a significantly small minority carrier diffusion length using the constant-magnitude surface-photovoltage (SPV) method. An unmodulated illumination provides the light excitation on the surface of the material to generate the SPV. A manually controlled or automatic servo system maintains a constant predetermined value of the SPV. A vibrating Kelvin method-type probe electrode couples the SPV to a measurement system. The operating optical wavelength of an adjustable monochromator to compensate for the wavelength dependent sensitivity of a photodetector is selected to measure the illumination intensity (photon flux) on the silicon. Measurements of the relative photon flux for a plurality of wavelengths are plotted against the reciprocal of the optical absorption coefficient of the material. A linear plot of the data points is extrapolated to zero intensity. The negative intercept value on the reciprocal optical coefficient axis of the extrapolated linear plot is the diffusion length of the minority carriers.

Extended quantification of the generalized recurrence plot

NASA Astrophysics Data System (ADS)

Riedl, Maik; Marwan, Norbert; Kurths, Jürgen

2016-04-01

The generalized recurrence plot is a modern tool for quantification of complex spatial patterns. Its application spans the analysis of trabecular bone structures, Turing structures, turbulent spatial plankton patterns, and fractals. But, it is also successfully applied to the description of spatio-temporal dynamics and the detection of regime shifts, such as in the complex Ginzburg-Landau- equation. The recurrence plot based determinism is a central measure in this framework quantifying the level of regularities in temporal and spatial structures. We extend this measure for the generalized recurrence plot considering additional operations of symmetry than the simple translation. It is tested not only on two-dimensional regular patterns and noise but also on complex spatial patterns reconstructing the parameter space of the complex Ginzburg-Landau-equation. The extended version of the determinism resulted in values which are consistent to the original recurrence plot approach. Furthermore, the proposed method allows a split of the determinism into parts which based on laminar and non-laminar regions of the two-dimensional pattern of the complex Ginzburg-Landau-equation. A comparison of these parts with a standard method of image classification, the co-occurrence matrix approach, shows differences especially in the description of patterns associated with turbulence. In that case, it seems that the extended version of the determinism allows a distinction of phase turbulence and defect turbulence by means of their spatial patterns. This ability of the proposed method promise new insights in other systems with turbulent dynamics coming from climatology, biology, ecology, and social sciences, for example.

Metaplot: A Novel Stata Graph for Assessing Heterogeneity at a Glance

PubMed Central

Poorolajal, J; Mahmoodi, M; Majdzadeh, R; Fotouhi, A

2010-01-01

Background: Heterogeneity is usually a major concern in meta-analysis. Although there are some statistical approaches for assessing variability across studies, here we present a new approach to heterogeneity using “MetaPlot” that investigate the influence of a single study on the overall heterogeneity. Methods: MetaPlot is a two-way (x, y) graph, which can be considered as a complementary graphical approach for testing heterogeneity. This method shows graphically as well as numerically the results of an influence analysis, in which Higgins’ I2 statistic with 95% (Confidence interval) CI are computed omitting one study in each turn and then are plotted against reciprocal of standard error (1/SE) or “precision”. In this graph, “1/SE” lies on x axis and “I2 results” lies on y axe. Results: Having a first glance at MetaPlot, one can predict to what extent omission of a single study may influence the overall heterogeneity. The precision on x-axis enables us to distinguish the size of each trial. The graph describes I2 statistic with 95% CI graphically as well as numerically in one view for prompt comparison. It is possible to implement MetaPlot for meta-analysis of different types of outcome data and summary measures. Conclusion: This method presents a simple graphical approach to identify an outlier and its effect on overall heterogeneity at a glance. We wish to suggest MetaPlot to Stata experts to prepare its module for the software. PMID:23113013

Zipper plot: visualizing transcriptional activity of genomic regions.

PubMed

Avila Cobos, Francisco; Anckaert, Jasper; Volders, Pieter-Jan; Everaert, Celine; Rombaut, Dries; Vandesompele, Jo; De Preter, Katleen; Mestdagh, Pieter

2017-05-02

Reconstructing transcript models from RNA-sequencing (RNA-seq) data and establishing these as independent transcriptional units can be a challenging task. Current state-of-the-art tools for long non-coding RNA (lncRNA) annotation are mainly based on evolutionary constraints, which may result in false negatives due to the overall limited conservation of lncRNAs. To tackle this problem we have developed the Zipper plot, a novel visualization and analysis method that enables users to simultaneously interrogate thousands of human putative transcription start sites (TSSs) in relation to various features that are indicative for transcriptional activity. These include publicly available CAGE-sequencing, ChIP-sequencing and DNase-sequencing datasets. Our method only requires three tab-separated fields (chromosome, genomic coordinate of the TSS and strand) as input and generates a report that includes a detailed summary table, a Zipper plot and several statistics derived from this plot. Using the Zipper plot, we found evidence of transcription for a set of well-characterized lncRNAs and observed that fewer mono-exonic lncRNAs have CAGE peaks overlapping with their TSSs compared to multi-exonic lncRNAs. Using publicly available RNA-seq data, we found more than one hundred cases where junction reads connected protein-coding gene exons with a downstream mono-exonic lncRNA, revealing the need for a careful evaluation of lncRNA 5'-boundaries. Our method is implemented using the statistical programming language R and is freely available as a webtool.

Comparison of visual-based helicopter and fixed-wing forward-looking infrared surveys for counting white-tailed deer Odocoileus virginianus

USGS Publications Warehouse

Storm, Daniel J.; Samuel, Michael D.; Van Deelen, Timothy R.; Malcolm, Karl D.; Rolley, Robert E.; Frost, Nancy A.; Bates, Donald P.; Richards, Bryan J.

2011-01-01

Aerial surveys using direct counts of animals are commonly used to estimate deer abundance. Forward-looking infrared (FLIR) technology is increasingly replacing traditional methods such as visual observation from helicopters. Our goals were to compare fixed-wing FLIR and visual, helicopter-based counts in terms of relative bias, influence of snow cover and cost. We surveyed five plots: four 41.4 km2 plots with free-ranging white-tailed deer Odocoileus virginianus populations in Wisconsin and a 5.3 km2 plot with a white-tailed deer population contained by a high fence in Michigan. We surveyed plots using both fixed-wing FLIR and helicopters, both with snow cover and without snow. None of the methods counted more deer than the other when snow was present. Helicopter counts were lower in the absence of snow, but lack of snow cover did not apparently affect FLIR. Group sizes of observed deer were similar regardless of survey method or season. We found that FLIR counts were generally precise (CV = 0.089) when two or three replicate surveys were conducted within a few hours. However, at the plot level, FLIR counts differed greatly between seasons, suggesting that detection rates vary over larger time scales. Fixed-wing FLIR was more costly than visual observers in helicopters and was more restrictive in terms of acceptable survey conditions. Further research is needed to understand what factors influence the detection of deer during FLIR surveys.

Analytical Determination of Fluoride Ion Using Gran's Semi-Antilog Plot.

ERIC Educational Resources Information Center

Barnhard, Ralph J.

1983-01-01

A quantitative determination for fluoride ion using a commercially available fluoride electrode is described. The procedure referred to as known-addition is employed with the data processed on Gran's Plot Paper. Background information, experimental procedures, and advantages/disadvantages of the method are discussed. (JN)

Quantification of metabotropic glutamate subtype 5 receptors in the brain by an equilibrium method using 18F-SP203.

PubMed

Kimura, Yasuyuki; Siméon, Fabrice G; Zoghbi, Sami S; Zhang, Yi; Hatazawa, Jun; Pike, Victor W; Innis, Robert B; Fujita, Masahiro

2012-02-01

A new PET ligand, 3-fluoro-5-(2-(2-(18)F-(fluoromethyl)-thiazol-4-yl)ethynyl)benzonitrile (18F-SP203) can quantify metabotropic glutamate subtype 5 receptors (mGluR5) in human brain by a bolus injection and kinetic modeling. As an alternative approach to a bolus injection, binding can simply be measured as a ratio of tissue to metabolite-corrected plasma at a single time point under equilibrium conditions achieved by administering the radioligand with a bolus injection followed by a constant infusion. The purpose of this study was to validate the equilibrium method as an alternative to the standard kinetic method for measuring 18F-SP203 binding in the brain. Nine healthy subjects were injected with 18F-SP203 using a bolus plus constant infusion for 300 min. A single ratio of bolus-to-constant infusion (the activity of bolus equaled to that of infusion over 219 min) was applied to all subjects to achieve equilibrium in approximately 120 min. As a measure of ligand binding, we compared total distribution volume (VT) calculated by the equilibrium and kinetic methods in each scan. The equilibrium method calculated VT by the ratio of radioactivity in the brain to the concentration of 18F-SP203 in arterial plasma at 120 min, and the kinetic method calculated VT by a two-tissue compartment model using brain and plasma dynamic data from 0 to 120 min. VT obtained via the equilibrium method was highly correlated with VT obtained via kinetic modeling. Inter-subject variability of VT obtained via the equilibrium method was slightly smaller than VT obtained via the kinetic method. VT obtained via the equilibrium method was ~10% higher than VT obtained via the kinetic method, indicating a small difference between the measurements. Taken together, the results of this study show that using the equilibrium method is an acceptable alternative to the standard kinetic method when using 18F-SP203 to measure mGluR5. Although small differences in the measurements obtained via the equilibrium and kinetic methods exist, both methods consistently measured mGluR5 as indicated by the highly correlated VT values; the equilibrium method was slightly more precise, as indirectly measured by the smaller coefficient of variability across subjects. In addition, when using 18F-SP203, the equilibrium method is more efficient because it requires much less data. Copyright © 2011. Published by Elsevier Inc.

Newer developments on self-modeling curve resolution implementing equality and unimodality constraints.

PubMed

Beyramysoltan, Samira; Abdollahi, Hamid; Rajkó, Róbert

2014-05-27

Analytical self-modeling curve resolution (SMCR) methods resolve data sets to a range of feasible solutions using only non-negative constraints. The Lawton-Sylvestre method was the first direct method to analyze a two-component system. It was generalized as a Borgen plot for determining the feasible regions in three-component systems. It seems that a geometrical view is required for considering curve resolution methods, because the complicated (only algebraic) conceptions caused a stop in the general study of Borgen's work for 20 years. Rajkó and István revised and elucidated the principles of existing theory in SMCR methods and subsequently introduced computational geometry tools for developing an algorithm to draw Borgen plots in three-component systems. These developments are theoretical inventions and the formulations are not always able to be given in close form or regularized formalism, especially for geometric descriptions, that is why several algorithms should have been developed and provided for even the theoretical deductions and determinations. In this study, analytical SMCR methods are revised and described using simple concepts. The details of a drawing algorithm for a developmental type of Borgen plot are given. Additionally, for the first time in the literature, equality and unimodality constraints are successfully implemented in the Lawton-Sylvestre method. To this end, a new state-of-the-art procedure is proposed to impose equality constraint in Borgen plots. Two- and three-component HPLC-DAD data set were simulated and analyzed by the new analytical curve resolution methods with and without additional constraints. Detailed descriptions and explanations are given based on the obtained abstract spaces. Copyright © 2014 Elsevier B.V. All rights reserved.

Comparison of Rain-Fast Bait Stations Versus Foliar Bait Sprays for Control of Oriental Fruit Fly, Bactrocera dorsalis, in Papaya Orchards in Hawaii

PubMed Central

Piñero, Jaime C.; Mau, Ronald F. L.; Vargas, Roger I.

2010-01-01

Bait stations represent an environmentally friendly attract-and-kill approach to fruit fly population suppression. Recently a novel, visually attractive, rain-fast bait station was developed in Hawaii for potential use against multiple species of pestiferous fruit flies. Here, we compared the efficacy of GF-120 NF Naturalyte Fruit Fly Bait applied either as foliar sprays or onto bait stations in reducing female oriental fruit fly, Bactrocera dorsalis (Hendel) (Diptera: Tephritidae), population density and level of fruit infestation in commercial papaya orchards in Hawaii. Trapping and infestation data were used as indicators of the effectiveness of the two bait application methods. For the first 10 weeks of the study, captures of female B. dorsalis in monitoring traps were significantly greater in control plots than in plots treated with foliar sprays or bait stations. Six weeks after the first bait spray, incidence of infestation (i.e. number of fruit with one or more B. dorsalis larvae) of quarter to half-ripe papaya fruit was reduced by 71.4% and 63.1% for plots with bait stations and foliar sprays, respectively, as compared to control plots. Twelve weeks after first spray, incidence of infestation was reduced by only 54.5% and 45.4% for plots with bait stations and foliar sprays, respectively, as compared to control plots. About 42% less GF-120 was used in orchard plots with bait stations compared to those subject to foliar sprays. The impact of field sanitation on the outcome is also discussed. The results indicate that bait stations can provide a simple, efficient, and economical method of applying insecticidal baits to control fruit flies and a safer alternative to foliar sprays. PMID:21067423

Metaplot: a novel stata graph for assessing heterogeneity at a glance.

PubMed

Poorolajal, J; Mahmoodi, M; Majdzadeh, R; Fotouhi, A

2010-01-01

Heterogeneity is usually a major concern in meta-analysis. Although there are some statistical approaches for assessing variability across studies, here we present a new approach to heterogeneity using "MetaPlot" that investigate the influence of a single study on the overall heterogeneity. MetaPlot is a two-way (x, y) graph, which can be considered as a complementary graphical approach for testing heterogeneity. This method shows graphically as well as numerically the results of an influence analysis, in which Higgins' I(2) statistic with 95% (Confidence interval) CI are computed omitting one study in each turn and then are plotted against reciprocal of standard error (1/SE) or "precision". In this graph, "1/SE" lies on x axis and "I(2) results" lies on y axe. Having a first glance at MetaPlot, one can predict to what extent omission of a single study may influence the overall heterogeneity. The precision on x-axis enables us to distinguish the size of each trial. The graph describes I(2) statistic with 95% CI graphically as well as numerically in one view for prompt comparison. It is possible to implement MetaPlot for meta-analysis of different types of outcome data and summary measures. This method presents a simple graphical approach to identify an outlier and its effect on overall heterogeneity at a glance. We wish to suggest MetaPlot to Stata experts to prepare its module for the software.

QUESPOWR MRI: QUantification of Exchange as a function of Saturation Power On the Water Resonance

PubMed Central

Randtke, Edward A.; Pagel, Mark D.; Cárdenas-Rodríguez, Julio

2018-01-01

QUantification of Exchange as a function of Saturation Power On the Water Resonance (QUESPOWR) MRI is a new method that can estimate chemical exchange rates. This method acquires a series of OPARACHEE MRI acquisitions with a range of RF powers for the WALTZ16* pulse train, which are applied on the water resonance. A QUESPOWR plot can be generated from the power dependence of the % water signal, which is similar to a QUESP plot that is generated from CEST MRI acquisition methods with RF saturation applied off-resonance from water. A QUESPOWR plot can be quantitatively analyzed using linear fitting methods to provide estimates of average chemical exchange rates. Analyses of the shapes of QUESPOWR plots can also be used to estimate relative differences in average chemical exchange rates and concentrations of biomolecules. The performance of QUESPOWR MRI was assessed via simulations, an in vitro study with iopamidol, and an in vivo study with a mouse model of mammary carcinoma. The results showed that QUESPOWR MRI is especially sensitive to chemical exchange between water and biomolecules that have intermediate to fast chemical exchange rates and chemical shifts that are close to water, which are notoriously difficult to assess with other CEST MRI methods. In addition, in vivo QUESPOWR MRI detected acidic tumor tissues relative to normal tissues that are pH-neutral, and therefore may be a new paradigm for tumor detection with MRI. PMID:27404128

Application of GPS and Near-Surface Geophysical Methods to Evaluate Agricultural Test Plot Differences

USDA-ARS?s Scientific Manuscript database

A field research facility with two pairs of replicated agricultural test plots (four total) was established at a location in northwest Ohio during 2005 for the purpose of studying water table management strategies. Initial efforts at this field research facility were devoted to evaluating difference...

Michigan's forests, 2004: statistics and quality assurance

Treesearch

Scott A. Pugh; Mark H. Hansen; Gary Brand; Ronald E. McRoberts

2010-01-01

The first annual inventory of Michigan's forests was completed in 2004 after 18,916 plots were selected and 10,355 forested plots were visited. This report includes detailed information on forest inventory methods, quality of estimates, and additional tables. An earlier publication presented analyses of the inventoried data (Pugh et al. 2009).

A note on the generation of phase plane plots on a digital computer. [for solution of nonlinear differential equations

NASA Technical Reports Server (NTRS)

Simon, M. K.

1980-01-01

A technique is presented for generating phase plane plots on a digital computer which circumvents the difficulties associated with more traditional methods of numerical solving nonlinear differential equations. In particular, the nonlinear differential equation of operation is formulated.

Methods of cutting ponderosa pine in the Southwest - Establishment report: Even-aged yield study, Plot 11

Treesearch

Gilbert H. Schubert

1963-01-01

The objectie of the study is to obtain information on the growth and yield of even-aged stands of different stocking levels. The plot will also serve as the start of a detailed growing stock study for the ponderosa pine region.

Plotting landscape perspectives of clearcut units.

Treesearch

Roger H. Twito

1978-01-01

The aesthetics of clearcut units potentially visible from a distance can be improved by judicious design. Screening clearcuts from view or shaping them to characterize natural openings are current methods used for this purpose. Perspective plots illustrating how proposed clearcut units will look from specific off-site viewing points provide an...

Plot Description (PD)

Treesearch

Robert E. Keane

2006-01-01

The Plot Description (PD) form is used to describe general characteristics of the FIREMON macroplot to provide ecological context for data analyses. The PD data characterize the topographical setting, geographic reference point, general plant composition and cover, ground cover, fuels, and soils information. This method provides the general ecological data that can be...

Plotit-method of interactively plotting input data for the vorlax computer program. [computerized aircraft configuration design

NASA Technical Reports Server (NTRS)

Denn, F. M.

1978-01-01

Geometric input plotting to the VORLAX computer program by means of an interactive remote terminal is reported. The software consists of a procedure file and two programs. The programs and procedure file are described and a sample execution is presented.

Normal probability plots with confidence.

PubMed

Chantarangsi, Wanpen; Liu, Wei; Bretz, Frank; Kiatsupaibul, Seksan; Hayter, Anthony J; Wan, Fang

2015-01-01

Normal probability plots are widely used as a statistical tool for assessing whether an observed simple random sample is drawn from a normally distributed population. The users, however, have to judge subjectively, if no objective rule is provided, whether the plotted points fall close to a straight line. In this paper, we focus on how a normal probability plot can be augmented by intervals for all the points so that, if the population distribution is normal, then all the points should fall into the corresponding intervals simultaneously with probability 1-α. These simultaneous 1-α probability intervals provide therefore an objective mean to judge whether the plotted points fall close to the straight line: the plotted points fall close to the straight line if and only if all the points fall into the corresponding intervals. The powers of several normal probability plot based (graphical) tests and the most popular nongraphical Anderson-Darling and Shapiro-Wilk tests are compared by simulation. Based on this comparison, recommendations are given in Section 3 on which graphical tests should be used in what circumstances. An example is provided to illustrate the methods. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Change of physical and chemical composition of soil washing out during vegetation season from differently used fields

NASA Astrophysics Data System (ADS)

Baryła, A.; Pierzgalski, E.; Karczmarczyk, A.

2009-04-01

oil losses due to water erosion not only decrease of soil fertility but also influence on pollution of water bodies. One of the method for limitation of water erosion process is protected soil management and choose suitable plants which requires knowledge about effect and mechanism of erosion under different environmental conditions. The results of measurements of quantity and quality of soil losses from three experimental plots are given in the article. Plots were located in Experimental Agricultural Station Puczniew in central part of Poland. Surface soil layer on the plots had mechanical composition of medium loam soil. On two plots grass and barley were planted. Third plot was used as fallow and tilled land. Measurements were carried out four times in the period May-October 2007. Physical and chemical composition of washed soil material was analyzed.

Gene features selection for three-class disease classification via multiple orthogonal partial least square discriminant analysis and S-plot using microarray data.

PubMed

Yang, Mingxing; Li, Xiumin; Li, Zhibin; Ou, Zhimin; Liu, Ming; Liu, Suhuan; Li, Xuejun; Yang, Shuyu

2013-01-01

DNA microarray analysis is characterized by obtaining a large number of gene variables from a small number of observations. Cluster analysis is widely used to analyze DNA microarray data to make classification and diagnosis of disease. Because there are so many irrelevant and insignificant genes in a dataset, a feature selection approach must be employed in data analysis. The performance of cluster analysis of this high-throughput data depends on whether the feature selection approach chooses the most relevant genes associated with disease classes. Here we proposed a new method using multiple Orthogonal Partial Least Squares-Discriminant Analysis (mOPLS-DA) models and S-plots to select the most relevant genes to conduct three-class disease classification and prediction. We tested our method using Golub's leukemia microarray data. For three classes with subtypes, we proposed hierarchical orthogonal partial least squares-discriminant analysis (OPLS-DA) models and S-plots to select features for two main classes and their subtypes. For three classes in parallel, we employed three OPLS-DA models and S-plots to choose marker genes for each class. The power of feature selection to classify and predict three-class disease was evaluated using cluster analysis. Further, the general performance of our method was tested using four public datasets and compared with those of four other feature selection methods. The results revealed that our method effectively selected the most relevant features for disease classification and prediction, and its performance was better than that of the other methods.

The effect of poultry manure application rate and AlCl(3) treatment on bacterial fecal indicators in runoff.

PubMed

Brooks, J P; Adeli, A; McLaughlin, M R; Miles, D M

2012-12-01

Increasing costs associated with inorganic fertilizer have led to widespread use of broiler litter. Proper land application, typically limiting nutrient loss, is essential to protect surface water. This study was designed to evaluate litter-borne microbial runoff (heterotrophic plate count bacteria, staphylococci, Escherichia coli, enterococci, and Clostridium perfringens) while applying typical nutrient-control methods. Field studies were conducted in which plots with high and low litter rates, inorganic fertilizer, AlCl(3)-treated litter, and controls were rained on five times using a rain generator. Overall, microbial runoff from poultry litter applied plots was consistently greater (2-5 log(10) plot(-1)) than controls. No appreciable effect on microbial runoff was noted from variable litter application rate or AlCl(3) treatments, though rain event, not time, significantly affected runoff load. C. perfringens and staphylococci runoff were consistently associated with poultry litter application, during early rain events, while other indicators were unreliable. Large microbial runoff pulses were observed, ranging from 10(2) to 10(10) CFU plot(-1); however, only a small fraction of litter-borne microbes were recoverable in runoff. This study indicated that microbial runoff from litter-applied plots can be substantial, and that methods intended to reduce nutrient losses do not necessarily reduce microbial runoff.

Protein Folding Mechanism of the Dimeric AmphiphysinII/Bin1 N-BAR Domain

PubMed Central

Gruber, Tobias; Balbach, Jochen

2015-01-01

The human AmphyphisinII/Bin1 N-BAR domain belongs to the BAR domain superfamily, whose members sense and generate membrane curvatures. The N-BAR domain is a 57 kDa homodimeric protein comprising a six helix bundle. Here we report the protein folding mechanism of this protein as a representative of this protein superfamily. The concentration dependent thermodynamic stability was studied by urea equilibrium transition curves followed by fluorescence and far-UV CD spectroscopy. Kinetic unfolding and refolding experiments, including rapid double and triple mixing techniques, allowed to unravel the complex folding behavior of N-BAR. The equilibrium unfolding transition curve can be described by a two-state process, while the folding kinetics show four refolding phases, an additional burst reaction and two unfolding phases. All fast refolding phases show a rollover in the chevron plot but only one of these phases depends on the protein concentration reporting the dimerization step. Secondary structure formation occurs during the three fast refolding phases. The slowest phase can be assigned to a proline isomerization. All kinetic experiments were also followed by fluorescence anisotropy detection to verify the assignment of the dimerization step to the respective folding phase. Based on these experiments we propose for N-BAR two parallel folding pathways towards the homodimeric native state depending on the proline conformation in the unfolded state. PMID:26368922

Identification of a key structural element for protein folding within beta-hairpin turns.

PubMed

Kim, Jaewon; Brych, Stephen R; Lee, Jihun; Logan, Timothy M; Blaber, Michael

2003-05-09

Specific residues in a polypeptide may be key contributors to the stability and foldability of the unique native structure. Identification and prediction of such residues is, therefore, an important area of investigation in solving the protein folding problem. Atypical main-chain conformations can help identify strains within a folded protein, and by inference, positions where unique amino acids may have a naturally high frequency of occurrence due to favorable contributions to stability and folding. Non-Gly residues located near the left-handed alpha-helical region (L-alpha) of the Ramachandran plot are a potential indicator of structural strain. Although many investigators have studied mutations at such positions, no consistent energetic or kinetic contributions to stability or folding have been elucidated. Here we report a study of the effects of Gly, Ala and Asn substitutions found within the L-alpha region at a characteristic position in defined beta-hairpin turns within human acidic fibroblast growth factor, and demonstrate consistent effects upon stability and folding kinetics. The thermodynamic and kinetic data are compared to available data for similar mutations in other proteins, with excellent agreement. The results have identified that Gly at the i+3 position within a subset of beta-hairpin turns is a key contributor towards increasing the rate of folding to the native state of the polypeptide while leaving the rate of unfolding largely unchanged.

Role of deuterium desorption kinetics on the thermionic emission properties of polycrystalline diamond films with respect to kinetic isotope effects

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

Paxton, W. F., E-mail: william.f.paxton@vanderbilt.edu; Howell, M.; Kang, W. P.

2014-06-21

The desorption kinetics of deuterium from polycrystalline chemical vapor deposited diamond films were characterized by monitoring the isothermal thermionic emission current behavior. The reaction was observed to follow a first-order trend as evidenced by the decay rate of the thermionic emission current over time which is in agreement with previously reported studies. However, an Arrhenius plot of the reaction rates at each tested temperature did not exhibit the typical linear behavior which appears to contradict past observations of the hydrogen (or deuterium) desorption reaction from diamond. This observed deviation from linearity, specifically at lower temperatures, has been attributed to non-classicalmore » processes. Though no known previous studies reported similar deviations, a reanalysis of the data obtained in the present study was performed to account for tunneling which appeared to add merit to this hypothesis. Additional investigations were performed by reevaluating previously reported data involving the desorption of hydrogen (as opposed to deuterium) from diamond which further indicated this reaction to be dominated by tunneling at the temperatures tested in this study (<775 °C). An activation energy of 3.19 eV and a pre-exponential constant of 2.3 × 10{sup 12} s{sup −1} were determined for the desorption reaction of deuterium from diamond which is in agreement with previously reported studies.« less

Kinetics and Thermodynamics of DNA Processing by Wild Type DNA-Glycosylase Endo III and Its Catalytically Inactive Mutant Forms.

PubMed

Kladova, Olga A; Krasnoperov, Lev N; Kuznetsov, Nikita A; Fedorova, Olga S

2018-03-30

Endonuclease III (Endo III or Nth) is one of the key enzymes responsible for initiating the base excision repair of oxidized or reduced pyrimidine bases in DNA. In this study, a thermodynamic analysis of structural rearrangements of the specific and nonspecific DNA-duplexes during their interaction with Endo III is performed based on stopped-flow kinetic data. 1,3-diaza-2-oxophenoxazine (tC O ), a fluorescent analog of the natural nucleobase cytosine, is used to record multistep DNA binding and lesion recognition within a temperature range (5-37 °C). Standard Gibbs energy, enthalpy, and entropy of the specific steps are derived from kinetic data using Van't Hoff plots. The data suggest that enthalpy-driven exothermic 5,6-dihydrouracil (DHU) recognition and desolvation-accompanied entropy-driven adjustment of the enzyme-substrate complex into a catalytically active state play equally important parts in the overall process. The roles of catalytically significant amino acids Lys120 and Asp138 in the DNA lesion recognition and catalysis are identified. Lys120 participates not only in the catalytic steps but also in the processes of local duplex distortion, whereas substitution Asp138Ala leads to a complete loss of the ability of Endo III to distort a DNA double chain during enzyme-DNA complex formation.

Estimation of Free Radical Ionization Energies by the Kinetic Method and the Relationship between the Kinetic Method and the Hammett Equation.

PubMed

Chen, G; Wong, P; Cooks, R G

1997-09-01

Substituted 1,2-diphenylethanes undergo competitive dissociations upon electron ionization (EI) to generate substituted benzyl cation and benzyl radical pairs. Application of the kinetic method to the previous reported EI mass spectra of these covalently bound precursor ions (data are taken from McLafferty et al. J. Am. Chem. Soc. 1970, 92, 6867)) is used to estimate the ionization energies of substituted benzyl free radicals. A correlation is observed between the Hammett σ constant of the substituents and the kinetic method parameter, ln(k(x)/k(H)), where k(x) is the rate of fragmentation to give the substituted product ion and k(H) is the rate to give the benzyl ion itself. Systems involving weakly bound cluster ions, including proton-bound dimers of meta- and para-substituted pyridines and meta- and para-substituted anilines, and electron-bound dimers of meta- and para-substituted nitrobenzenes, also show good correlations between the kinetic method parameter and the Hammett σ constant.

Preparation and characterization of corn cob activated carbon coated with nano-sized magnetite particles for the removal of Cr(VI).

PubMed

Nethaji, S; Sivasamy, A; Mandal, A B

2013-04-01

Activated carbon prepared from corn cob biomass, magnetized by magnetite nanoparticles (MCCAC) was used for the adsorption of hexavalent chromium from aqueous solution. The adsorbent was characterized by SEM, TEM, XRD, VSM, surface functionality and zero-point charge. The iron oxide nanoparticles were of 50 nm sizes and the saturation magnetization value for the adsorbent is 48.43 emu/g. Adsorption was maximum at pH 2. Isotherm data were modeled using Langmuir, Freundlich and Temkin isotherm. The prepared MCCAC had a heterogeneous surface. The maximum monolayer adsorption capacity was 57.37 mg/g. Kinetic studies were carried out and the data fitted the pseudo second-order equation. The mechanism of the adsorption process was studied by incorporating the kinetic data with intraparticle diffusion model, Bangham equation and Boyd plot. The adsorption was by chemisorption and the external mass transfer was the rate-determining step. A micro column was designed and the basic column parameters were estimated. Copyright © 2013 Elsevier Ltd. All rights reserved.

"First-principles" kinetic Monte Carlo simulations revisited: CO oxidation over RuO2 (110).

PubMed

Hess, Franziska; Farkas, Attila; Seitsonen, Ari P; Over, Herbert

2012-03-15

First principles-based kinetic Monte Carlo (kMC) simulations are performed for the CO oxidation on RuO(2) (110) under steady-state reaction conditions. The simulations include a set of elementary reaction steps with activation energies taken from three different ab initio density functional theory studies. Critical comparison of the simulation results reveals that already small variations in the activation energies lead to distinctly different reaction scenarios on the surface, even to the point where the dominating elementary reaction step is substituted by another one. For a critical assessment of the chosen energy parameters, it is not sufficient to compare kMC simulations only to experimental turnover frequency (TOF) as a function of the reactant feed ratio. More appropriate benchmarks for kMC simulations are the actual distribution of reactants on the catalyst's surface during steady-state reaction, as determined by in situ infrared spectroscopy and in situ scanning tunneling microscopy, and the temperature dependence of TOF in the from of Arrhenius plots. Copyright © 2012 Wiley Periodicals, Inc.

Facile synthesis, biological evaluation and molecular docking studies of novel substituted azole derivatives

NASA Astrophysics Data System (ADS)

Rafiq, Muhammad; Saleem, Muhammad; Jabeen, Farukh; Hanif, Muhammad; Seo, Sung-Yum; Kang, Sung Kwon; Lee, Ki Hwan

2017-06-01

In this study, we synthesized the series of novel azole derivatives and evaluated for enzyme inhibition assays, corresponding kinetic analysis and molecular modeling. Among the investigated bioassays, the oxadiazole derivatives 4a-k were found potent α-glucosidase inhibitors while the Schiff base derivatives 7a-k exhibited considerable potential toward urease inhibition. The inhibition kinetics for the most active compounds were analyzed by the Lineweaver-Burk plots to investigate the possible binding modes of the synthesized compounds toward the tested proteins. Moreover, the detailed docking studies were performed on the synthesized library of 4a-k and 7a-k to study the molecular interaction and binding mode in the active site of the modeled yeast α-glucosidase and Jack Bean Urease, respectively. It could be inferred from docking results that theoretical studies are in close agreement to that of the experimental results. The structure of one of the compound 7k was characterized by the single crystal X-ray diffraction analysis in order to find out the predominant conformation of the molecules.

Aldose Reductase Inhibitory Activity of Compounds from  Zea mays L.

PubMed Central

Kim, Tae Hyeon; Kim, Jin Kyu; Kang, Young-Hee; Lee, Jae-Yong; Kang, Il Jun; Lim, Soon Sung

2013-01-01

Aldose reductase (AR) inhibitors have a considerable therapeutic potential against diabetes complications and do not increase the risk of hypoglycemia. Through bioassay-guided fractionation of an EtOH extract of the kernel from purple corn (Zea mays L.), 7 nonanthocyanin phenolic compounds (compound 1–7) and 5 anthocyanins (compound 8–12) were isolated. These compounds were investigated by rat lens aldose reductase (RLAR) inhibitory assays. Kinetic analyses of recombinant human aldose reductase (rhAR) were performed, and intracellular galactitol levels were measured. Hirsutrin, one of 12 isolated compounds, showed the most potent RLAR inhibitory activity (IC50, 4.78 μM). In the kinetic analyses using Lineweaver-Burk plots of 1/velocity and 1/substrate concentration, hirsutrin showed competitive inhibition against rhAR. Furthermore, hirsutrin inhibited galactitol formation in rat lens and erythrocytes sample incubated with a high concentration of galactose; this finding indicates that hirsutrin may effectively prevent osmotic stress in hyperglycemia. Therefore, hirsutrin derived from Zea mays L. may be a potential therapeutic agent against diabetes complications. PMID:23586057

Strategies for minimizing sample size for use in airborne LiDAR-based forest inventory

USGS Publications Warehouse

Junttila, Virpi; Finley, Andrew O.; Bradford, John B.; Kauranne, Tuomo

2013-01-01

Recently airborne Light Detection And Ranging (LiDAR) has emerged as a highly accurate remote sensing modality to be used in operational scale forest inventories. Inventories conducted with the help of LiDAR are most often model-based, i.e. they use variables derived from LiDAR point clouds as the predictive variables that are to be calibrated using field plots. The measurement of the necessary field plots is a time-consuming and statistically sensitive process. Because of this, current practice often presumes hundreds of plots to be collected. But since these plots are only used to calibrate regression models, it should be possible to minimize the number of plots needed by carefully selecting the plots to be measured. In the current study, we compare several systematic and random methods for calibration plot selection, with the specific aim that they be used in LiDAR based regression models for forest parameters, especially above-ground biomass. The primary criteria compared are based on both spatial representativity as well as on their coverage of the variability of the forest features measured. In the former case, it is important also to take into account spatial auto-correlation between the plots. The results indicate that choosing the plots in a way that ensures ample coverage of both spatial and feature space variability improves the performance of the corresponding models, and that adequate coverage of the variability in the feature space is the most important condition that should be met by the set of plots collected.

Spectral method for a kinetic swarming model

DOE PAGES

Gamba, Irene M.; Haack, Jeffrey R.; Motsch, Sebastien

2015-04-28

Here we present the first numerical method for a kinetic description of the Vicsek swarming model. The kinetic model poses a unique challenge, as there is a distribution dependent collision invariant to satisfy when computing the interaction term. We use a spectral representation linked with a discrete constrained optimization to compute these interactions. To test the numerical scheme we investigate the kinetic model at different scales and compare the solution with the microscopic and macroscopic descriptions of the Vicsek model. Lastly, we observe that the kinetic model captures key features such as vortex formation and traveling waves.

Methods for Kinetic and Thermodynamic Analysis of Aminoacyl-tRNA Synthetases

PubMed Central

Francklyn, Christopher S.; First, Eric A.; Perona, John J.; Hou, Ya-Ming

2008-01-01

The accuracy of protein synthesis relies on the ability of aminoacyl-tRNA synthetases (aaRSs) to discriminate among true and near cognate substrates. To date, analysis of aaRSs function, including identification of residues of aaRS participating in amino acid and tRNA discrimination, has largely relied on the steady state kinetic pyrophosphate exchange and aminoacylation assays. Pre-steady state kinetic studies investigating a more limited set of aaRS systems have also been undertaken to assess the energetic contributions of individual enzyme-substrate interactions, particularly in the adenylation half reaction. More recently, a renewed interest in the use of rapid kinetics approaches for aaRSs has led to their application to several new aaRS systems, resulting in the identification of mechanistic differences that distinguish the two structurally distinct aaRS classes. Here, we review the techniques for thermodynamic and kinetic analysis of aaRS function. Following a brief survey of methods for the preparation of materials and for steady state kinetic analysis, this review will describe pre-steady state kinetic methods employing rapid quench and stopped-flow fluorescence for analysis of the activation and aminoacyl transfer reactions. Application of these methods to any aaRS system allows the investigator to derive detailed kinetic mechanisms for the activation and aminoacyl transfer reactions, permitting issues of substrate specificity, stereochemical mechanism, and inhibitor interaction to be addressed in a rigorous and quantitative fashion. PMID:18241792

Mayday - integrative analytics for expression data

PubMed Central

2010-01-01

Background DNA Microarrays have become the standard method for large scale analyses of gene expression and epigenomics. The increasing complexity and inherent noisiness of the generated data makes visual data exploration ever more important. Fast deployment of new methods as well as a combination of predefined, easy to apply methods with programmer's access to the data are important requirements for any analysis framework. Mayday is an open source platform with emphasis on visual data exploration and analysis. Many built-in methods for clustering, machine learning and classification are provided for dissecting complex datasets. Plugins can easily be written to extend Mayday's functionality in a large number of ways. As Java program, Mayday is platform-independent and can be used as Java WebStart application without any installation. Mayday can import data from several file formats, database connectivity is included for efficient data organization. Numerous interactive visualization tools, including box plots, profile plots, principal component plots and a heatmap are available, can be enhanced with metadata and exported as publication quality vector files. Results We have rewritten large parts of Mayday's core to make it more efficient and ready for future developments. Among the large number of new plugins are an automated processing framework, dynamic filtering, new and efficient clustering methods, a machine learning module and database connectivity. Extensive manual data analysis can be done using an inbuilt R terminal and an integrated SQL querying interface. Our visualization framework has become more powerful, new plot types have been added and existing plots improved. Conclusions We present a major extension of Mayday, a very versatile open-source framework for efficient micro array data analysis designed for biologists and bioinformaticians. Most everyday tasks are already covered. The large number of available plugins as well as the extension possibilities using compiled plugins and ad-hoc scripting allow for the rapid adaption of Mayday also to very specialized data exploration. Mayday is available at http://microarray-analysis.org. PMID:20214778

[Enzyme kinetic glucose determination by the glucose dehydrogenase method. Enzyme kinetic substrate determination using competitive inhibitors, II (author's transl)].

PubMed

Müller-Matthesius, R

1975-05-01

The sensitivity of enzyme kinetic substrate determinations can be improved with the aid of competitive inhibitors. As an example, the determination of glucose dehydrogenase in the presence of potassium thiocyanate is described. The method has the advantage of rapid operation with satisfactory precision.

MONALISA for stochastic simulations of Petri net models of biochemical systems.

PubMed

Balazki, Pavel; Lindauer, Klaus; Einloft, Jens; Ackermann, Jörg; Koch, Ina

2015-07-10

The concept of Petri nets (PN) is widely used in systems biology and allows modeling of complex biochemical systems like metabolic systems, signal transduction pathways, and gene expression networks. In particular, PN allows the topological analysis based on structural properties, which is important and useful when quantitative (kinetic) data are incomplete or unknown. Knowing the kinetic parameters, the simulation of time evolution of such models can help to study the dynamic behavior of the underlying system. If the number of involved entities (molecules) is low, a stochastic simulation should be preferred against the classical deterministic approach of solving ordinary differential equations. The Stochastic Simulation Algorithm (SSA) is a common method for such simulations. The combination of the qualitative and semi-quantitative PN modeling and stochastic analysis techniques provides a valuable approach in the field of systems biology. Here, we describe the implementation of stochastic analysis in a PN environment. We extended MONALISA - an open-source software for creation, visualization and analysis of PN - by several stochastic simulation methods. The simulation module offers four simulation modes, among them the stochastic mode with constant firing rates and Gillespie's algorithm as exact and approximate versions. The simulator is operated by a user-friendly graphical interface and accepts input data such as concentrations and reaction rate constants that are common parameters in the biological context. The key features of the simulation module are visualization of simulation, interactive plotting, export of results into a text file, mathematical expressions for describing simulation parameters, and up to 500 parallel simulations of the same parameter sets. To illustrate the method we discuss a model for insulin receptor recycling as case study. We present a software that combines the modeling power of Petri nets with stochastic simulation of dynamic processes in a user-friendly environment supported by an intuitive graphical interface. The program offers a valuable alternative to modeling, using ordinary differential equations, especially when simulating single-cell experiments with low molecule counts. The ability to use mathematical expressions provides an additional flexibility in describing the simulation parameters. The open-source distribution allows further extensions by third-party developers. The software is cross-platform and is licensed under the Artistic License 2.0.

Inferring the demographic history from DNA sequences: An importance sampling approach based on non-homogeneous processes.

PubMed

Ait Kaci Azzou, S; Larribe, F; Froda, S

2016-10-01

In Ait Kaci Azzou et al. (2015) we introduced an Importance Sampling (IS) approach for estimating the demographic history of a sample of DNA sequences, the skywis plot. More precisely, we proposed a new nonparametric estimate of a population size that changes over time. We showed on simulated data that the skywis plot can work well in typical situations where the effective population size does not undergo very steep changes. In this paper, we introduce an iterative procedure which extends the previous method and gives good estimates under such rapid variations. In the iterative calibrated skywis plot we approximate the effective population size by a piecewise constant function, whose values are re-estimated at each step. These piecewise constant functions are used to generate the waiting times of non homogeneous Poisson processes related to a coalescent process with mutation under a variable population size model. Moreover, the present IS procedure is based on a modified version of the Stephens and Donnelly (2000) proposal distribution. Finally, we apply the iterative calibrated skywis plot method to a simulated data set from a rapidly expanding exponential model, and we show that the method based on this new IS strategy correctly reconstructs the demographic history. Copyright © 2016. Published by Elsevier Inc.

Extraction kinetic modelling of total polyphenols and total anthocyanins from saffron floral bio-residues: Comparison of extraction methods.

PubMed

Da Porto, Carla; Natolino, Andrea

2018-08-30

Analysis of the extraction kinetic modelling for natural compounds is essential for industrial application. The second order rate model was applied to estimate the extraction kinetics of conventional solid-liquid extraction (CSLE), ultrasound-assisted extraction (UAE) and microwave-assisted extraction (MAE) of total polyphenols (TPC) from saffron floral bio-residues at different solid-to-liquid ratios (R S/L )(1:10, 1:20, 1:30, 1:50 g ml -1 ), ethanol 59% as solvent and 66 °C temperature. The optimum solid-to-liquid ratios for TPC kinetics were 1:20 for CLSE, 1:30 for UAE and 1:50 for MAE. The kinetics of total anthocyanins (TA) and antioxidant activity (AA) were investigated for the optimum R S/L for each method. The results showed a good prediction of the model for extraction kinetics in all experiments (R 2  > 0.99; NRMS 0.65-3.35%). The kinetic parameters were calculated and discussed. UAE, compared with the other methods, had the greater efficiency for TPC, TA and AA. Copyright © 2018 Elsevier Ltd. All rights reserved.

Validation of Bayesian analysis of compartmental kinetic models in medical imaging.

PubMed

Sitek, Arkadiusz; Li, Quanzheng; El Fakhri, Georges; Alpert, Nathaniel M

2016-10-01

Kinetic compartmental analysis is frequently used to compute physiologically relevant quantitative values from time series of images. In this paper, a new approach based on Bayesian analysis to obtain information about these parameters is presented and validated. The closed-form of the posterior distribution of kinetic parameters is derived with a hierarchical prior to model the standard deviation of normally distributed noise. Markov chain Monte Carlo methods are used for numerical estimation of the posterior distribution. Computer simulations of the kinetics of F18-fluorodeoxyglucose (FDG) are used to demonstrate drawing statistical inferences about kinetic parameters and to validate the theory and implementation. Additionally, point estimates of kinetic parameters and covariance of those estimates are determined using the classical non-linear least squares approach. Posteriors obtained using methods proposed in this work are accurate as no significant deviation from the expected shape of the posterior was found (one-sided P>0.08). It is demonstrated that the results obtained by the standard non-linear least-square methods fail to provide accurate estimation of uncertainty for the same data set (P<0.0001). The results of this work validate new methods for a computer simulations of FDG kinetics. Results show that in situations where the classical approach fails in accurate estimation of uncertainty, Bayesian estimation provides an accurate information about the uncertainties in the parameters. Although a particular example of FDG kinetics was used in the paper, the methods can be extended for different pharmaceuticals and imaging modalities. Copyright © 2016 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

The Influence of Clocking Angle of the Projectile on the Simulated Impact Response of a Shuttle Leading Edge Wing Panel

NASA Technical Reports Server (NTRS)

Jackson, Karen E.; Fasanella, Edwin L.; Lyle, Karen H.; Spellman, Regina L.

2005-01-01

An analytical study was conducted to determine the influence of clocking angle of a foam projectile impacting a space shuttle leading edge wing panel. Four simulations were performed using LS-DYNA. The leading edge panels are fabricated of multiple layers of reinforced carbon-carbon (RCC) material. The RCC material was represented using Mat 58, which is a material property that can be used for laminated composite fabrics. Simulations were performed of a rectangular-shaped foam block, weighing 0.23-lb., impacting RCC Panel 9 on the top surface. The material properties of the foam were input using Mat 83. The impact velocity was 1,000 ft/s along the Orbiter X-axis. In two models, the foam impacted on a corner, in one model the foam impacted the panel initially on the 2-in.-long edge, and in the last model the foam impacted the panel on the 7-in.- long edge. The simulation results are presented as contour plots of first principal infinitesimal strain and time history plots of contact force and internal and kinetic energy of the foam and RCC panel.

Temperature effect on bacterial azo bond reduction kinetics: an Arrhenius plot analysis.

PubMed

Angelova, Blaga; Avramova, Tatyana; Stefanova, Lilyana; Mutafov, Sava

2008-06-01

Studied was the effect of temperature in the range 12-46 degrees C on the rate of bacterial decolorization of the mono-azo dye Acid Orange 7 by Alcaligenes faecalis 6132 and Rhodococcus erythropolis 24. With both strains the raise of temperature led to a corresponding raise of decolorization rate better manifested by R. erythropolis. The analysis of the Arrhenius plot revealed a break near the middle of the temperature range. The regression analysis showed practically complete identity of the observed break point temperatures (T (BP)): 20.7 degrees C for Alc. faecalis and 20.8 degrees C for R. erythropolis. The values of the activation energy of the decolorization reaction (E (a)) were found to depend on both the organism and the temperature range. In the range below T (BP) the estimated values of E (a) were 138 +/- 7 kJ mol(-1) for Alc. faecalis and 160 +/- 8 kJ mol(-1) for R. erythropolis. In the range above T (BP) they were 54.2 +/- 1.8 kJ mol(-1) for Alc. faecalis and 37.6 +/- 4.1 kJ mol(-1) for R. erythropolis. Discussed are the possible reasons for the observed abrupt change of the activation energy.

Characterizing the Severe Turbulence Environments Associated With Commercial Aviation Accidents: A Real-Time Turbulence Model (RTTM) Designed for the Operational Prediction of Hazardous Aviation Turbulence Environments

NASA Technical Reports Server (NTRS)

Kaplan, Michael L.; Lux, Kevin M.; Cetola, Jeffrey D.; Huffman, Allan W.; Riordan, Allen J.; Slusser, Sarah W.; Lin, Yuh-Lang; Charney, Joseph J.; Waight, Kenneth T.

2004-01-01

Real-time prediction of environments predisposed to producing moderate-severe aviation turbulence is studied. We describe the numerical model and its postprocessing system designed for said prediction of environments predisposed to severe aviation turbulence as well as presenting numerous examples of its utility. The numerical model is MASS version 5.13, which is integrated over three different grid matrices in real time on a university work station in support of NASA Langley Research Center s B-757 turbulence research flight missions. The postprocessing system includes several turbulence-related products, including four turbulence forecasting indices, winds, streamlines, turbulence kinetic energy, and Richardson numbers. Additionally, there are convective products including precipitation, cloud height, cloud mass fluxes, lifted index, and K-index. Furthermore, soundings, sounding parameters, and Froude number plots are also provided. The horizontal cross-section plot products are provided from 16 000 to 46 000 ft in 2000-ft intervals. Products are available every 3 hours at the 60- and 30-km grid interval and every 1.5 hours at the 15-km grid interval. The model is initialized from the NWS ETA analyses and integrated two times a day.

Fundamental electrode kinetics

NASA Technical Reports Server (NTRS)

Elder, J. P.

1968-01-01

Report presents the fundamentals of electrode kinetics and the methods used in evaluating the characteristic parameters of rapid-charge transfer processes at electrode-electrolyte interfaces. The concept of electrode kinetics is outlined, followed by the principles underlying the experimental techniques for the investigation of electrode kinetics.

A Program for Calculating and Plotting Synthetic Common-Source Seismic-Reflection Traces for Multilayered Earth Models.

ERIC Educational Resources Information Center

Ramananantoandro, Ramanantsoa

1988-01-01

Presented is a description of a BASIC program to be used on an IBM microcomputer for calculating and plotting synthetic seismic-reflection traces for multilayered earth models. Discusses finding raypaths for given source-receiver offsets using the "shooting method" and calculating the corresponding travel times. (Author/CW)

A regression-adjusted approach can estimate competing biomass

Treesearch

James H. Miller

1983-01-01

A method is presented for estimating above-ground herbaceous and woody biomass on competition research plots. On a set of destructively-sampled plots, an ocular estimate of biomass by vegetative component is first made, after which vegetation is clipped, dried, and weighed. Linear regressions are then calculated for each component between estimated and actual weights...

Application of GPS and Near-Surface Geophysical Methods to Evaluate Differences Between Agricultural Test Plots

USDA-ARS?s Scientific Manuscript database

A field research facility with two pairs of replicated agricultural test plots (four total) was established at a location in northwest Ohio during 2005 for the purpose of studying water table management strategies. Initial efforts at this field research facility were devoted to evaluating difference...

Prefield methods: streamlining forest or nonforest determinations to increase inventory efficiency

Treesearch

Sara Goeking; Gretchen Moisen; Kevin Megown; Jason Toombs

2009-01-01

Interior West Forest Inventory and Analysis has developed prefield protocols to distinguish forested plots that require field visits from nonforested plots that do not require field visits. Recent innovations have increased the efficiency of the prefield process. First, the incorporation of periodic inventory data into a prefield database increased the amount of...

Continuum of risk analysis methods to assess tillage system sustainability at the experimental plot level

USDA-ARS?s Scientific Manuscript database

The primary goal of this study was to evaluate the efficacy of stochastic dominance and stochastic efficiency with respect to a function (SERF) methodology for ranking conventional and conservation tillage systems using 14 years (1990-2003) of economic budget data collected from 36 plots at the Iowa...

The Wally plot approach to assess the calibration of clinical prediction models.

PubMed

Blanche, Paul; Gerds, Thomas A; Ekstrøm, Claus T

2017-12-06

A prediction model is calibrated if, roughly, for any percentage x we can expect that x subjects out of 100 experience the event among all subjects that have a predicted risk of x%. Typically, the calibration assumption is assessed graphically but in practice it is often challenging to judge whether a "disappointing" calibration plot is the consequence of a departure from the calibration assumption, or alternatively just "bad luck" due to sampling variability. We propose a graphical approach which enables the visualization of how much a calibration plot agrees with the calibration assumption to address this issue. The approach is mainly based on the idea of generating new plots which mimic the available data under the calibration assumption. The method handles the common non-trivial situations in which the data contain censored observations and occurrences of competing events. This is done by building on ideas from constrained non-parametric maximum likelihood estimation methods. Two examples from large cohort data illustrate our proposal. The 'wally' R package is provided to make the methodology easily usable.

Occurrence of dead core in catalytic particles containing immobilized enzymes: analysis for the Michaelis-Menten kinetics and assessment of numerical methods.

PubMed

Pereira, Félix Monteiro; Oliveira, Samuel Conceição

2016-11-01

In this article, the occurrence of dead core in catalytic particles containing immobilized enzymes is analyzed for the Michaelis-Menten kinetics. An assessment of numerical methods is performed to solve the boundary value problem generated by the mathematical modeling of diffusion and reaction processes under steady state and isothermal conditions. Two classes of numerical methods were employed: shooting and collocation. The shooting method used the ode function from Scilab software. The collocation methods included: that implemented by the bvode function of Scilab, the orthogonal collocation, and the orthogonal collocation on finite elements. The methods were validated for simplified forms of the Michaelis-Menten equation (zero-order and first-order kinetics), for which analytical solutions are available. Among the methods covered in this article, the orthogonal collocation on finite elements proved to be the most robust and efficient method to solve the boundary value problem concerning Michaelis-Menten kinetics. For this enzyme kinetics, it was found that the dead core can occur when verified certain conditions of diffusion-reaction within the catalytic particle. The application of the concepts and methods presented in this study will allow for a more generalized analysis and more accurate designs of heterogeneous enzymatic reactors.

Peptide kinetics from picoseconds to microseconds using boxed molecular dynamics: Power law rate coefficients in cyclisation reactions

NASA Astrophysics Data System (ADS)

Shalashilin, Dmitrii V.; Beddard, Godfrey S.; Paci, Emanuele; Glowacki, David R.

2012-10-01

Molecular dynamics (MD) methods are increasingly widespread, but simulation of rare events in complex molecular systems remains a challenge. We recently introduced the boxed molecular dynamics (BXD) method, which accelerates rare events, and simultaneously provides both kinetic and thermodynamic information. We illustrate how the BXD method may be used to obtain high-resolution kinetic data from explicit MD simulations, spanning picoseconds to microseconds. The method is applied to investigate the loop formation dynamics and kinetics of cyclisation for a range of polypeptides, and recovers a power law dependence of the instantaneous rate coefficient over six orders of magnitude in time, in good agreement with experimental observations. Analysis of our BXD results shows that this power law behaviour arises when there is a broad and nearly uniform spectrum of reaction rate coefficients. For the systems investigated in this work, where the free energy surfaces have relatively small barriers, the kinetics is very sensitive to the initial conditions: strongly non-equilibrium conditions give rise to power law kinetics, while equilibrium initial conditions result in a rate coefficient with only a weak dependence on time. These results suggest that BXD may offer us a powerful and general algorithm for describing kinetics and thermodynamics in chemical and biochemical systems.

Calibrated Passive Sampling--Multi-plot Field Measurements of NH3 Emissions with a Combination of Dynamic Tube Method and Passive Samplers.

PubMed

Pacholski, Andreas

2016-03-21

Agricultural ammonia (NH3) emissions (90% of total EU emissions) are responsible for about 45% airborne eutrophication, 31% soil acidification and 12% fine dust formation within the EU15. But NH3 emissions also mean a considerable loss of nutrients. Many studies on NH3 emission from organic and mineral fertilizer application have been performed in recent decades. Nevertheless, research related to NH3 emissions after application fertilizers is still limited in particular with respect to relationships to emissions, fertilizer type, site conditions and crop growth. Due to the variable response of crops to treatments, effects can only be validated in experimental designs including field replication for statistical testing. The dominating ammonia loss methods yielding quantitative emissions require large field areas, expensive equipment or current supply, which restricts their application in replicated field trials. This protocol describes a new methodology for the measurement of NH3 emissions on many plots linking a simple semi-quantitative measuring method used in all plots, with a quantitative method by simultaneous measurements using both methods on selected plots. As a semi-quantitative measurement method passive samplers are used. The second method is a dynamic chamber method (Dynamic Tube Method) to obtain a transfer quotient, which converts the semi-quantitative losses of the passive sampler to quantitative losses (kg nitrogen ha(-1)). The principle underlying this approach is that passive samplers placed in a homogeneous experimental field have the same NH3 absorption behavior under identical environmental conditions. Therefore, a transfer co-efficient obtained from single passive samplers can be used to scale the values of all passive samplers used in the same field trial. The method proved valid under a wide range of experimental conditions and is recommended to be used under conditions with bare soil or small canopies (<0.3 m). Results obtained from experiments with taller plants should be treated more carefully.

Calibrated Passive Sampling - Multi-plot Field Measurements of NH3 Emissions with a Combination of Dynamic Tube Method and Passive Samplers

PubMed Central

Pacholski, Andreas

2016-01-01

Agricultural ammonia (NH3) emissions (90% of total EU emissions) are responsible for about 45% airborne eutrophication, 31% soil acidification and 12% fine dust formation within the EU15. But NH3 emissions also mean a considerable loss of nutrients. Many studies on NH3 emission from organic and mineral fertilizer application have been performed in recent decades. Nevertheless, research related to NH3 emissions after application fertilizers is still limited in particular with respect to relationships to emissions, fertilizer type, site conditions and crop growth. Due to the variable response of crops to treatments, effects can only be validated in experimental designs including field replication for statistical testing. The dominating ammonia loss methods yielding quantitative emissions require large field areas, expensive equipment or current supply, which restricts their application in replicated field trials. This protocol describes a new methodology for the measurement of NH3 emissions on many plots linking a simple semi-quantitative measuring method used in all plots, with a quantitative method by simultaneous measurements using both methods on selected plots. As a semi-quantitative measurement method passive samplers are used. The second method is a dynamic chamber method (Dynamic Tube Method) to obtain a transfer quotient, which converts the semi-quantitative losses of the passive sampler to quantitative losses (kg nitrogen ha-1). The principle underlying this approach is that passive samplers placed in a homogeneous experimental field have the same NH3 absorption behavior under identical environmental conditions. Therefore, a transfer co-efficient obtained from single passive samplers can be used to scale the values of all passive samplers used in the same field trial. The method proved valid under a wide range of experimental conditions and is recommended to be used under conditions with bare soil or small canopies (<0.3 m). Results obtained from experiments with taller plants should be treated more carefully. PMID:27023010

Comparative kinetics and reciprocal inhibition of nitrate and nitrite uptake in roots of uninduced and induced barley (Hordeum vulgare L.) seedlings

NASA Technical Reports Server (NTRS)

Aslam, M.; Travis, R. L.; Huffaker, R. C.

1992-01-01

Nitrate and NO2- transport by roots of 8-day-old uninduced and induced intact barley (Hordeum vulgare L. var CM 72) seedlings were compared to kinetic patterns, reciprocal inhibition of the transport systems, and the effect of the inhibitor, p-hydroxymercuribenzoate. Net uptake of NO3- and NO2- was measured by following the depletion of the ions from the uptake solutions. The roots of uninduced seedlings possessed a low concentration, saturable, low Km, possibly a constitutive uptake system, and a linear system for both NO3- and NO2-. The low Km system followed Michaelis-Menten kinetics and approached saturation between 40 and 100 micromolar, whereas the linear system was detected between 100 and 500 micromolar. In roots of induced seedlings, rates for both NO3- and NO2- uptake followed Michaelis-Menten kinetics and approached saturation at about 200 micromolar. In induced roots, two kinetically identifiable transport systems were resolved for each anion. At the lower substrate concentrations, less than 10 micromolar, the apparent low Kms of NO3- and NO2- uptake were 7 and 9 micromolar, respectively, and were similar to those of the low Km system in uninduced roots. At substrate concentrations between 10 and 200 micromolar, the apparent high Km values of NO3- uptake ranged from 34 to 36 micromolar and of NO2- uptake ranged from 41 to 49 micromolar. A linear system was also found in induced seedlings at concentrations above 500 micromolar. Double reciprocal plots indicated that NO3- and NO2- inhibited the uptake of each other competitively in both uninduced and induced seedlings; however, Ki values showed that NO3- was a more effective inhibitor than NO2-. Nitrate and NO2- transport by both the low and high Km systems were greatly inhibited by p-hydroxymercuribenzoate, whereas the linear system was only slightly inhibited.

Kinetics of low-temperature transitions and a reaction rate theory from non-equilibrium distributions

PubMed Central

Aquilanti, Vincenzo; Coutinho, Nayara Dantas

2017-01-01

This article surveys the empirical information which originated both by laboratory experiments and by computational simulations, and expands previous understanding of the rates of chemical processes in the low-temperature range, where deviations from linearity of Arrhenius plots were revealed. The phenomenological two-parameter Arrhenius equation requires improvement for applications where interpolation or extrapolations are demanded in various areas of modern science. Based on Tolman's theorem, the dependence of the reciprocal of the apparent activation energy as a function of reciprocal absolute temperature permits the introduction of a deviation parameter d covering uniformly a variety of rate processes, from those where quantum mechanical tunnelling is significant and d < 0, to those where d > 0, corresponding to the Pareto–Tsallis statistical weights: these generalize the Boltzmann–Gibbs weight, which is recovered for d = 0. It is shown here how the weights arise, relaxing the thermodynamic equilibrium limit, either for a binomial distribution if d > 0 or for a negative binomial distribution if d < 0, formally corresponding to Fermion-like or Boson-like statistics, respectively. The current status of the phenomenology is illustrated emphasizing case studies; specifically (i) the super-Arrhenius kinetics, where transport phenomena accelerate processes as the temperature increases; (ii) the sub-Arrhenius kinetics, where quantum mechanical tunnelling propitiates low-temperature reactivity; (iii) the anti-Arrhenius kinetics, where processes with no energetic obstacles are rate-limited by molecular reorientation requirements. Particular attention is given for case (i) to the treatment of diffusion and viscosity, for case (ii) to formulation of a transition rate theory for chemical kinetics including quantum mechanical tunnelling, and for case (iii) to the stereodirectional specificity of the dynamics of reactions strongly hindered by the increase of temperature. This article is part of the themed issue ‘Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces’. PMID:28320904

Kinetics of low-temperature transitions and a reaction rate theory from non-equilibrium distributions.

PubMed

Aquilanti, Vincenzo; Coutinho, Nayara Dantas; Carvalho-Silva, Valter Henrique

2017-04-28

This article surveys the empirical information which originated both by laboratory experiments and by computational simulations, and expands previous understanding of the rates of chemical processes in the low-temperature range, where deviations from linearity of Arrhenius plots were revealed. The phenomenological two-parameter Arrhenius equation requires improvement for applications where interpolation or extrapolations are demanded in various areas of modern science. Based on Tolman's theorem, the dependence of the reciprocal of the apparent activation energy as a function of reciprocal absolute temperature permits the introduction of a deviation parameter d covering uniformly a variety of rate processes, from those where quantum mechanical tunnelling is significant and d  < 0, to those where d  > 0, corresponding to the Pareto-Tsallis statistical weights: these generalize the Boltzmann-Gibbs weight, which is recovered for d  = 0. It is shown here how the weights arise, relaxing the thermodynamic equilibrium limit, either for a binomial distribution if d  > 0 or for a negative binomial distribution if d  < 0, formally corresponding to Fermion-like or Boson-like statistics, respectively. The current status of the phenomenology is illustrated emphasizing case studies; specifically (i) the super -Arrhenius kinetics, where transport phenomena accelerate processes as the temperature increases; (ii) the sub -Arrhenius kinetics, where quantum mechanical tunnelling propitiates low-temperature reactivity; (iii) the anti -Arrhenius kinetics, where processes with no energetic obstacles are rate-limited by molecular reorientation requirements. Particular attention is given for case (i) to the treatment of diffusion and viscosity, for case (ii) to formulation of a transition rate theory for chemical kinetics including quantum mechanical tunnelling, and for case (iii) to the stereodirectional specificity of the dynamics of reactions strongly hindered by the increase of temperature.This article is part of the themed issue 'Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces'. © 2017 The Author(s).

Kinetics of Organic Transformations Under Mild Aqueous Conditions: Implications for the Origin of Life and Its Metabolism

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

2003-01-01

The rates of thermal transformation of organic molecules containing carbon, hydrogen, and oxygen were systematically examined in order to identify the kinetic constraints that governed origin-of-life organic chemistry under mild aqueous conditions. Arrhenius plots of the kinetic data were used to estimate the reaction half-life at 50 C, and to reveal the effect of functional groups on reactivity. This survey showed that hydrocarbons and organic substances containing a single oxygenated group were kinetically the most stable (i. e. acetate decarboxylation half-life was l0(exp 18) years at 50 C); whereas, organic substances containing two oxygenated groups in which one group was a beta-positioned carbonyl group were the most reactive (i. e. acetoacetate decarboxylation half-life was l0(exp-2) years at 50 C). Of all functional groups the beta-positioned carbonyl group (aldehyde or ketone) was the strongest activating group, giving rates of reaction that were up to 10(exp 24)-times faster than rates of similar molecules lacking the beta-carbonyl group. From this knowledge of organic reactivity and the inherent constraints of autocatalytic processes, we concluded that an origins-of-life process based on autocatalytic transformation of C,H,O-substrates was constrained to using the most reactive organic molecules that contain alpha- or beta-carbonyl groups, since small autocatalytic domains of plausible catalytic power that used less reactive substrates could not carry out chemical transformations fast enough to prevent catastrophic efflux (escape) of reaction intermediates. Knowledge of the kinetics of organic transformations is useful, not only in constraining the chemistry of the earliest autocatalytic process related to the origin of life, but also in establishing the relative reactivity of organic molecules on the early Earth and other planets that may or may not be related to the origin of life.

Collapse kinetics and chevron plots from simulations of denaturant-dependent folding of globular proteins

PubMed Central

Liu, Zhenxing; Reddy, Govardhan; O’Brien, Edward P.; Thirumalai, D.

2011-01-01

Quantitative description of how proteins fold under experimental conditions remains a challenging problem. Experiments often use urea and guanidinium chloride to study folding whereas the natural variable in simulations is temperature. To bridge the gap, we use the molecular transfer model that combines measured denaturant-dependent transfer free energies for the peptide group and amino acid residues, and a coarse-grained Cα-side chain model for polypeptide chains to simulate the folding of src SH3 domain. Stability of the native state decreases linearly as [C] (the concentration of guanidinium chloride) increases with the slope, m, that is in excellent agreement with experiments. Remarkably, the calculated folding rate at [C] = 0 is only 16-fold larger than the measured value. Most importantly ln kobs (kobs is the sum of folding and unfolding rates) as a function of [C] has the characteristic V (chevron) shape. In every folding trajectory, the times for reaching the native state, interactions stabilizing all the substructures, and global collapse coincide. The value of (mf is the slope of the folding arm of the chevron plot) is identical to the fraction of buried solvent accessible surface area in the structures of the transition state ensemble. In the dominant transition state, which does not vary significantly at low [C], the core of the protein and certain loops are structured. Besides solving the long-standing problem of computing the chevron plot, our work lays the foundation for incorporating denaturant effects in a physically transparent manner either in all-atom or coarse-grained simulations. PMID:21512127

Collapse kinetics and chevron plots from simulations of denaturant-dependent folding of globular proteins.

PubMed

Liu, Zhenxing; Reddy, Govardhan; O'Brien, Edward P; Thirumalai, D

2011-05-10

Quantitative description of how proteins fold under experimental conditions remains a challenging problem. Experiments often use urea and guanidinium chloride to study folding whereas the natural variable in simulations is temperature. To bridge the gap, we use the molecular transfer model that combines measured denaturant-dependent transfer free energies for the peptide group and amino acid residues, and a coarse-grained C(α)-side chain model for polypeptide chains to simulate the folding of src SH(3) domain. Stability of the native state decreases linearly as [C] (the concentration of guanidinium chloride) increases with the slope, m, that is in excellent agreement with experiments. Remarkably, the calculated folding rate at [C] = 0 is only 16-fold larger than the measured value. Most importantly ln k(obs) (k(obs) is the sum of folding and unfolding rates) as a function of [C] has the characteristic V (chevron) shape. In every folding trajectory, the times for reaching the native state, interactions stabilizing all the substructures, and global collapse coincide. The value of (m(f) is the slope of the folding arm of the chevron plot) is identical to the fraction of buried solvent accessible surface area in the structures of the transition state ensemble. In the dominant transition state, which does not vary significantly at low [C], the core of the protein and certain loops are structured. Besides solving the long-standing problem of computing the chevron plot, our work lays the foundation for incorporating denaturant effects in a physically transparent manner either in all-atom or coarse-grained simulations.

The reaction pathway of membrane-bound rat liver mitochondrial monoamine oxidase

PubMed Central

Houslay, Miles D.; Tipton, Keith F.

1973-01-01

1. A preparation of a partly purified mitochondrial outer-membrane fraction suitable for kinetic investigations of monoamine oxidase is described. 2. An apparatus suitable for varying the O2 concentration in a spectrophotometer cuvette is described. 3. The reaction catalysed by the membrane-bound enzyme is shown to proceed by a double-displacement (Ping Pong) mechanism, and a formal mechanism is proposed. 4. KCN, NaN3, benzyl cyanide and 4-cyanophenol are shown to be reversible inhibitors of the enzyme. 5. The non-linear reciprocal plot obtained with impure preparations of benzylamine, which is typical of high substrate inhibition, is shown to be due to aldehyde contamination of the substrate. PMID:4778271

A BAYESIAN METHOD OF ESTIMATING KINETIC PARAMETERS FOR THE INACTIVATION OF CRYPTOSPORIDIUM PARVUM OOCYSTS WITH CHLORINE DIOXIDE AND OZONE

EPA Science Inventory

The main objective of this paper is to use Bayesian methods to estimate the kinetic parameters for the inactivation kinetics of Cryptosporidium parvum oocysts with chlorine dioxide or ozone which are characterized by the delayed Chick-Watson model, i.e., a lag phase or shoulder f...

Measurement of Enzyme Kinetics by Use of a Blood Glucometer: Hydrolysis of Sucrose and Lactose

ERIC Educational Resources Information Center

Heinzerling, Peter; Schrader, Frank; Schanze, Sascha

2012-01-01

An alternative analytical method for measuring the kinetic parameters of the enzymes invertase and lactase is described. Invertase hydrolyzes sucrose to glucose and fructose and lactase hydrolyzes lactose to glucose and galactose. In most enzyme kinetics studies, photometric methods or test strips are used to quantify the derivates of the…

Encounters with neighbours : current developments of concepts based on recurrence plots and their applications

NASA Astrophysics Data System (ADS)

Marwan, Norbert

2003-09-01

In this work, different aspects and applications of the recurrence plot analysis are presented. First, a comprehensive overview of recurrence plots and their quantification possibilities is given. New measures of complexity are defined by using geometrical structures of recurrence plots. These measures are capable to find chaos-chaos transitions in processes. Furthermore, a bivariate extension to cross recurrence plots is studied. Cross recurrence plots exhibit characteristic structures which can be used for the study of differences between two processes or for the alignment and search for matching sequences of two data series. The selected applications of the introduced techniques to various kind of data demonstrate their ability. Analysis of recurrence plots can be adopted to the specific problem and thus opens a wide field of potential applications. Regarding the quantification of recurrence plots, chaos-chaos transitions can be found in heart rate variability data before the onset of life threatening cardiac arrhythmias. This may be of importance for the therapy of such cardiac arrhythmias. The quantification of recurrence plots allows to study transitions in brain during cognitive experiments on the base of single trials. Traditionally, for the finding of these transitions the averaging of a collection of single trials is needed. Using cross recurrence plots, the existence of an El Niño/Southern Oscillation-like oscillation is traced in northwestern Argentina 34,000 yrs. ago. In further applications to geological data, cross recurrence plots are used for time scale alignment of different borehole data and for dating a geological profile with a reference data set. Additional examples from molecular biology and speech recognition emphasize the suitability of cross recurrence plots. Diese Arbeit beschäftigt sich mit verschiedenen Aspekten und Anwendungen von Recurrence Plots. Nach einer Übersicht über Methoden, die auf Recurrence Plots basieren, werden neue Komplexitätsmaße eingeführt, die geometrische Strukturen in den Recurrence Plots beschreiben. Diese neuen Maße erlauben die Identifikation von Chaos-Chaos-Übergängen in dynamischen Prozessen. In einem weiteren Schritt werden Cross Recurrence Plots eingeführt, mit denen zwei verschiedene Prozesse untersucht werden. Diese bivariate Analyse ermöglicht die Bewertung von Unterschieden zwischen zwei Prozessen oder das Anpassen der Zeitskalen von zwei Zeitreihen. Diese Technik kann auch genutzt werden, um ähnliche Abschnitte in zwei verschiedenen Datenreihen zu finden. Im Anschluß werden diese neuen Entwicklungen auf Daten verschiedener Art angewendet. Methoden, die auf Recurrence Plots basieren, können an die speziellen Probleme angepaßt werden, so daß viele weitere Anwendungen möglich sind. Durch die Anwendung der neu eingeführten Komplexitätsmaße können Chaos-Chaos-Übergänge in Herzschlagdaten vor dem Auftreten einer lebensbedrohlichen Herzrhythmusstörung festgestellt werden, was für die Entwicklung neuer Therapien dieser Herzrhythmusstörungen von Bedeutung sein könnte. In einem weiteren Beispiel, in dem EEG-Daten aus einem kognitiv orientierten Experiment untersucht werden, ermöglichen diese Komplexitätsmaße das Erkennen von spezifischen Reaktionen im Gehirn bereits in Einzeltests. Normalerweise können diese Reaktionen erst durch die Auswertung von vielen Einzeltests erkannt werden. Mit der Hilfe von Cross Recurrence Plots wird die Existenz einer klimatischen Zirkulation, die der heutigen El Niño/ Southern Oscillation sehr ähnlich ist, im Nordwesten Argentiniens vor etwa 34000 Jahren nachgewiesen. Außerdem können mit Cross Recurrence Plots die Zeitskalen verschiedener Bohrlochdaten aufeinander abgeglichen werden. Diese Methode kann auch dazu genutzt werden, ein geologisches Profil mit Hilfe eines Referenzprofiles mit bekannter Zeitskala zu datieren. Weitere Beispiele aus den Gebieten der Molekularbiologie und der Spracherkennung unterstreichen das Potential dieser Methode.

Electrochemistry of free chlorine and monochloramine and its relevance to the presence of Pb in drinking water.

PubMed

Rajasekharan, Vishnu V; Clark, Brandi N; Boonsalee, Sansanee; Switzer, Jay A

2007-06-15

The commonly used disinfectants in drinking water are free chlorine (in the form of HOCl/OCl-) and monochloramine (NH2Cl). While free chlorine reacts with natural organic matter in water to produce chlorinated hydrocarbon byproducts, there is also concern that NH2Cl may react with Pbto produce soluble Pb(II) products--leading to elevated Pb levels in drinking water. In this study, electrochemical methods are used to compare the thermodynamics and kinetics of the reduction of these two disinfectants. The standard reduction potential for NH2Cl/Cl- was estimated to be +1.45 V in acidic media and +0.74 V in alkaline media versus NHE using thermodynamic cycles. The kinetics of electroreduction of the two disinfectants was studied using an Au rotating disk electrode. The exchange current densities estimated from Koutecky-Levich plots were 8.2 x 10(-5) and 4.1 x 10(-5) A/cm2, and by low overpotential experiments were 7.5 +/- 0.3 x 10(-5) and 3.7 +/- 0.4 x 10(-5) A/cm2 for free chlorine and NH2Cl, respectively. The rate constantforthe electrochemical reduction of free chlorine at equilibrium is approximately twice as large as that for the reduction of NH2Cl. Equilibrium potential measurements show that free chlorine will oxidize Pb to PbO2 above pH 1.7, whereas NH2Cl will oxidize Pb to PbO2 only above about pH 9.5, if the total dissolved inorganic carbon (DIC) is 18 ppm. Hence, NH2Cl is not capable of producing a passivating PbO2 layer on Pb, and could lead to elevated levels of dissolved Pb in drinking water.

Leuconostoc Mesenteroides Growth in Food Products: Prediction and Sensitivity Analysis by Adaptive-Network-Based Fuzzy Inference Systems

PubMed Central

Wang, Hue-Yu; Wen, Ching-Feng; Chiu, Yu-Hsien; Lee, I-Nong; Kao, Hao-Yun; Lee, I-Chen; Ho, Wen-Hsien

2013-01-01

Background An adaptive-network-based fuzzy inference system (ANFIS) was compared with an artificial neural network (ANN) in terms of accuracy in predicting the combined effects of temperature (10.5 to 24.5°C), pH level (5.5 to 7.5), sodium chloride level (0.25% to 6.25%) and sodium nitrite level (0 to 200 ppm) on the growth rate of Leuconostoc mesenteroides under aerobic and anaerobic conditions. Methods The ANFIS and ANN models were compared in terms of six statistical indices calculated by comparing their prediction results with actual data: mean absolute percentage error (MAPE), root mean square error (RMSE), standard error of prediction percentage (SEP), bias factor (Bf), accuracy factor (Af), and absolute fraction of variance (R 2). Graphical plots were also used for model comparison. Conclusions The learning-based systems obtained encouraging prediction results. Sensitivity analyses of the four environmental factors showed that temperature and, to a lesser extent, NaCl had the most influence on accuracy in predicting the growth rate of Leuconostoc mesenteroides under aerobic and anaerobic conditions. The observed effectiveness of ANFIS for modeling microbial kinetic parameters confirms its potential use as a supplemental tool in predictive mycology. Comparisons between growth rates predicted by ANFIS and actual experimental data also confirmed the high accuracy of the Gaussian membership function in ANFIS. Comparisons of the six statistical indices under both aerobic and anaerobic conditions also showed that the ANFIS model was better than all ANN models in predicting the four kinetic parameters. Therefore, the ANFIS model is a valuable tool for quickly predicting the growth rate of Leuconostoc mesenteroides under aerobic and anaerobic conditions. PMID:23705023

Reaction kinetics and critical phenomena: iodination of acetone in isobutyric acid + water near the consolute point.

PubMed

Hu, Baichuan; Baird, James K

2010-01-14

The rate of iodination of acetone has been measured as a function of temperature in the binary solvent isobutyric acid (IBA) + water near the upper consolute point. The reaction mixture was prepared by the addition of acetone, iodine, and potassium iodide to IBA + water at its critical composition of 38.8 mass % IBA. The value of the critical temperature determined immediately after mixing was 25.43 degrees C. Aliquots were extracted from the mixture at regular intervals in order to follow the time course of the reaction. After dilution of the aliquot with water to quench the reaction, the concentration of triiodide ion was determined by the measurement of the optical density at a wavelength of 565 nm. These measurements showed that the kinetics were zeroth order. When at the end of 24 h the reaction had come to equilibrium, the critical temperature was determined again and found to be 24.83 degrees C. An Arrhenius plot of the temperature dependence of the observed rate constant, k(obs), was linear over the temperature range 27.00-38.00 degrees C, but between 25.43 and 27.00 degrees C, the values of k(obs) fell below the extrapolation of the Arrhenius line. This behavior is evidence in support of critical slowing down. Our experimental method and results are significant in three ways: (1) In contrast to in situ measurements of optical density, the determination of the optical density of diluted aliquots avoided any interference from critical opalescence. (2) The measured reaction rate exhibited critical slowing down. (3) The rate law was pseudo zeroth order both inside and outside the critical region, indicating that the reaction mechanism was unaffected by the presence of the critical point.

A Computational Model for Docking of Noncompetitive Neuraminidase Inhibitors and Probing their Binding Interactions with Neuraminidase of Influenza Virus H5N1.

PubMed

Chintakrindi, Anand S; Martis, Elvis A F; Gohil, Devanshi J; Kothari, Sweta T; Chowdhary, Abhay S; Coutinho, Evans C; Kanyalkar, Meena A

2016-01-01

With cases of emergence of drug resistance to the current competitive inhibitors of neuraminidase (NA) such as oseltamivir and zanamavir, there is a present need for an alternative approach in the treatment of avian influenza. With this in view, some flavones and chalcones were designed based on quercetin, the most active naturally occurring noncompetitive inhibitor. We attempt to understand the binding of quercetin to H5N1-NA, and synthetic analogs of quercetin namely flavones and its precursors the chalcones using computational tools. Molecular docking was done using Libdock. Molecular dynamics (MD) simulations were performed using Amber14. We synthesized the two compounds; their structures were confirmed by infrared spectroscopy, 1H-NMR, and mass spectrometry. These molecules were then tested for H5N1-NA inhibition and kinetics of inhibition. Molecular docking studies yielded two compounds i.e., 4'-methoxyflavone and 2'-hydroxy-4-methoxychalcone, as promising leads which identified them as binders of the 150-cavity of NA. Furthermore, MD simulation studies revealed that quercetin and the two compounds bind and hold the 150 loop in its open conformation, which ultimately perturbs the binding of sialic acid in the catalytic site. Estimation of the free energy of binding by MM-PBSA portrays quercetin as more potent than chalcone and flavone. These molecules were then determined as non-competitive inhibitors from the Lineweaver-Burk plots rendered from the enzyme kinetic studies. We conclude that non-competitive type of inhibition, as shown in this study, can serve as an effective method to block NA and evade the currently seen drug resistance.

Observations of eruption clouds from Sakura-zima volcano, Kyushu, Japan from Skylab 4

USGS Publications Warehouse

Friedman, J.D.; Heiken, G.; Randerson, D.; McKay, D.S.

1976-01-01

Hasselblad and Nikon stereographic photographs taken from Skylab between 9 June 1973 and 1 February 1974 give synoptic plan views of several entire eruption clouds emanating from Sakura-zima volcano in Kagoshima Bay, Kyushu, Japan. Analytical plots of these stereographic pairs, studied in combination with meteorological data, indicate that the eruption clouds did not penetrate the tropopause and thus did not create a stratospheric dust veil of long residence time. A horizontal eddy diffusivity of the order of 106 cm2 s-1 and a vertical eddy diffusivity of the order of 105 cm2 s-1 were calculated from the observed plume dimensions and from available meteorological data. These observations are the first, direct evidence that explosive eruption at an estimated energy level of about 1018 ergs per paroxysm may be too small under atmospheric conditions similar to those prevailing over Sakura-zima for volcanic effluents to penetrate low-level tropospheric temperature inversions and, consequently, the tropopause over northern middle latitudes. Maximum elevation of the volcanic clouds was determined to be 3.4 km. The cumulative thermal energy release in the rise of volcanic plumes for 385 observed explosive eruptions was estimated to be 1020 to 1021 ergs (1013 to 1014 J), but the entire thermal energy release associated with pyroclastic activity may be of the order of 2.5 ?? 1022 ergs (2.5 ?? 1015 J). Estimation of the kinetic energy component of explosive eruptions via satellite observation and meteorological consideration of eruption clouds is thus useful in volcanology as an alternative technique to confirm the kinetic energy estimates made by ground-based geological and geophysical methods, and to aid in construction of physical models of potential and historical tephra-fallout sectors with implications for volcano-hazard prediction. ?? 1976.

How Geochemistry Provides Habitability: A Case Study of Iron Oxidation

NASA Astrophysics Data System (ADS)

St Clair, B.; Shock, E.

2016-12-01

Two things have to be true for chemotrophic microbes to gain chemical energy from their environment. First, there must be a source of energy, provided by compounds in differing oxidation states that are out of thermodynamic equilibrium with one another. Second, there must be mechanistic difficulties that are keeping those compounds from reacting, preventing chemical energy from dissipating on its own. Using this energetic reference frame, geochemical habitability requires the combined presence of energy sources and kinetic barriers, which are determined by numerous variables including temperature, pH, and concentrations of reactants and products. Here we present habitable geochemical space visually as habitability diagrams. As an example, the pH and temperature ranges that can sustain life for a specific reaction can be delineated by the aforementioned kinetic and energetic boundaries, together with commonly attainable pH / temperatures of environments at Earth's surface. Other habitability diagrams can be constructed for any combination of relevant geochemical variables to better illustrate the inherently multidimensional problem. We have chosen iron oxidation reactions to illustrate this point, as kinetic and energetic boundaries can be found at conditions readily attainable in natural systems. By calculating energy availability (as affinity, A) in each system from compositional data where concentrations of all reactants and products are known, the energy boundary is defined by A=0. Evaluating the kinetic boundary means measuring the relative rates of the biotic and abiotic processes in situ, which we have done in Yellowstone hot springs, acid mine drainage in Arizona, and cold springs in the Swiss Alps. Many experiments have yielded biological rates, and all have yielded abiotic rates, which range from inconsequential to rates too rapid for biology to compete. These results encompass both sides of the kinetic boundary, defining its trajectory. When plotted in pH and T space, this boundary is pH 7.7 at 10°C but decreases to pH 5.5 at 90°C. This tool for visualizing habitability helps quantify extreme environments as those near the kinetic or thermodynamic limits.

Mathematical modelling for the drying method and smoothing drying rate using cubic spline for seaweed Kappaphycus Striatum variety Durian in a solar dryer

NASA Astrophysics Data System (ADS)

M Ali, M. K.; Ruslan, M. H.; Muthuvalu, M. S.; Wong, J.; Sulaiman, J.; Yasir, S. Md.

2014-06-01

The solar drying experiment of seaweed using Green V-Roof Hybrid Solar Drier (GVRHSD) was conducted in Semporna, Sabah under the metrological condition in Malaysia. Drying of sample seaweed in GVRHSD reduced the moisture content from about 93.4% to 8.2% in 4 days at average solar radiation of about 600W/m2 and mass flow rate about 0.5 kg/s. Generally the plots of drying rate need more smoothing compared moisture content data. Special cares is needed at low drying rates and moisture contents. It is shown the cubic spline (CS) have been found to be effective for moisture-time curves. The idea of this method consists of an approximation of data by a CS regression having first and second derivatives. The analytical differentiation of the spline regression permits the determination of instantaneous rate. The method of minimization of the functional of average risk was used successfully to solve the problem. This method permits to obtain the instantaneous rate to be obtained directly from the experimental data. The drying kinetics was fitted with six published exponential thin layer drying models. The models were fitted using the coefficient of determination (R2), and root mean square error (RMSE). The modeling of models using raw data tested with the possible of exponential drying method. The result showed that the model from Two Term was found to be the best models describe the drying behavior. Besides that, the drying rate smoothed using CS shows to be effective method for moisture-time curves good estimators as well as for the missing moisture content data of seaweed Kappaphycus Striatum Variety Durian in Solar Dryer under the condition tested.

Stability-indicating assay of repaglinide in bulk and optimized nanoemulsion by validated high performance thin layer chromatography technique.

PubMed

Akhtar, Juber; Fareed, Sheeba; Aqil, Mohd

2013-07-01

A sensitive, selective, precise and stability-indicating high-performance thin-layer chromatographic (HPTLC) method for analysis of repaglinide both as a bulk drug and in nanoemulsion formulation was developed and validated. The method employed TLC aluminum plates precoated with silica gel 60F-254 as the stationary phase. The solvent system consisted of chloroform/methanol/ammonia/glacial acetic acid (7.5:1.5:0.9:0.1, v/v/v/v). This system was found to give compact spots for repaglinide (R f value of 0.38 ± 0.02). Repaglinide was subjected to acid and alkali hydrolysis, oxidation, photodegradation and dry heat treatment. Also, the degraded products were well separated from the pure drug. Densitometric analysis of repaglinide was carried out in the absorbance mode at 240 nm. The linear regression data for the calibration plots showed good linear relationship with r (2)= 0.998 ± 0.032 in the concentration range of 50-800 ng. The method was validated for precision, accuracy as recovery, robustness and specificity. The limits of detection and quantitation were 0.023 and 0.069 ng per spot, respectively. The drug undergoes degradation under acidic and basic conditions, oxidation and dry heat treatment. All the peaks of the degraded product were resolved from the standard drug with significantly different R f values. Statistical analysis proves that the method is reproducible and selective for the estimation of the said drug. As the method could effectively separate the drug from its degradation products, it can be employed as a stability-indicating one. Moreover, the proposed HPTLC method was utilized to investigate the degradation kinetics in 1M NaOH.

Mathematical modelling for the drying method and smoothing drying rate using cubic spline for seaweed Kappaphycus Striatum variety Durian in a solar dryer

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

M Ali, M. K., E-mail: majidkhankhan@ymail.com, E-mail: eutoco@gmail.com; Ruslan, M. H., E-mail: majidkhankhan@ymail.com, E-mail: eutoco@gmail.com; Muthuvalu, M. S., E-mail: sudaram-@yahoo.com, E-mail: jumat@ums.edu.my

2014-06-19

The solar drying experiment of seaweed using Green V-Roof Hybrid Solar Drier (GVRHSD) was conducted in Semporna, Sabah under the metrological condition in Malaysia. Drying of sample seaweed in GVRHSD reduced the moisture content from about 93.4% to 8.2% in 4 days at average solar radiation of about 600W/m{sup 2} and mass flow rate about 0.5 kg/s. Generally the plots of drying rate need more smoothing compared moisture content data. Special cares is needed at low drying rates and moisture contents. It is shown the cubic spline (CS) have been found to be effective for moisture-time curves. The idea ofmore » this method consists of an approximation of data by a CS regression having first and second derivatives. The analytical differentiation of the spline regression permits the determination of instantaneous rate. The method of minimization of the functional of average risk was used successfully to solve the problem. This method permits to obtain the instantaneous rate to be obtained directly from the experimental data. The drying kinetics was fitted with six published exponential thin layer drying models. The models were fitted using the coefficient of determination (R{sup 2}), and root mean square error (RMSE). The modeling of models using raw data tested with the possible of exponential drying method. The result showed that the model from Two Term was found to be the best models describe the drying behavior. Besides that, the drying rate smoothed using CS shows to be effective method for moisture-time curves good estimators as well as for the missing moisture content data of seaweed Kappaphycus Striatum Variety Durian in Solar Dryer under the condition tested.« less

Structural investigation of oxovanadium(IV) Schiff base complexes: X-ray crystallography, electrochemistry and kinetic of thermal decomposition.

PubMed

Asadi, Mozaffar; Asadi, Zahra; Savaripoor, Nooshin; Dusek, Michal; Eigner, Vaclav; Shorkaei, Mohammad Ranjkesh; Sedaghat, Moslem

2015-02-05

A series of new VO(IV) complexes of tetradentate N2O2 Schiff base ligands (L(1)-L(4)), were synthesized and characterized by FT-IR, UV-vis and elemental analysis. The structure of the complex VOL(1)⋅DMF was also investigated by X-ray crystallography which revealed a vanadyl center with distorted octahedral coordination where the 2-aza and 2-oxo coordinating sites of the ligand were perpendicular to the "-yl" oxygen. The electrochemical properties of the vanadyl complexes were investigated by cyclic voltammetry. A good correlation was observed between the oxidation potentials and the electron withdrawing character of the substituents on the Schiff base ligands, showing the following trend: MeO5-H>5-Br>5-Cl. Furthermore, the kinetic parameters of thermal decomposition were calculated by using the Coats-Redfern equation. According to the Coats-Redfern plots the kinetics of thermal decomposition of studied complexes is of the first-order in all stages, the free energy of activation for each following stage is larger than the previous one and the complexes have good thermal stability. The preparation of VOL(1)⋅DMF yielded also another compound, one kind of vanadium oxide [VO]X, with different habitus of crystals, (platelet instead of prisma) and without L(1) ligand, consisting of a V10O28 cage, diaminium moiety and dimethylamonium as a counter ions. Because its crystal structure was also new, we reported it along with the targeted complex. Copyright © 2014 Elsevier B.V. All rights reserved.

Disproportionation of a crystalline citrate salt of a developmental pharmaceutical compound: characterization of the kinetics using pH monitoring and online Raman spectroscopy plus quantitation of the crystalline free base form in binary physical mixtures using FT-Raman, XRPD and DSC.

PubMed

Skrdla, Peter J; Zhang, Dan

2014-03-01

The crystalline citrate salt (CS) of a developmental pharmaceutical compound, MK-Q, was investigated in this work from two different, but related, perspectives. In the first part of the paper, the apparent disproportionation kinetics were surveyed using two different slurry systems, one containing water and the other a pH 6.9 phosphate buffer, using time-dependent measurements of the solution pH or by acquiring online Raman spectra of the solids. While the CS is generally stable when stored as a solid under ambient conditions of temperature and humidity, its low pHmax (<3) facilitates rapid disproportionation in aqueous solution, particularly at higher pH values. The rate of disappearance of the CS was found to obey first-order (Noyes-Whitney/dissolution rate-limited) kinetics, however, the formation of the crystalline product form in the slurry system was observed to exhibit kinetics consistent with a heterogeneous nucleation-and-growth mechanism. In the second part of this paper, more sensitive offline measurements made using XRPD, DSC and FT-Raman spectroscopy were applied to the characterization of binary physical mixtures of the CS and free base (FB) crystalline forms of MK-Q to obtain a calibration curve for each technique. It was found that all calibration plots exhibited good linearity of response, with the limit of detection (LOD) for each technique estimated to be ≤7 wt% FB. While additional calibration curves would need to be constructed to allow for accurate quantitation in various slurry systems, the general feasibility of these techniques is demonstrated for detecting low levels of CS disproportionation. Copyright © 2013 Elsevier B.V. All rights reserved.

Serum hepcidin-25 may replace the ferritin index in the Thomas plot in assessing iron status in anemic patients.

PubMed

Thomas, C; Kobold, U; Balan, S; Roeddiger, R; Thomas, L

2011-04-01

Biochemical markers of iron deficiency do not distinguish iron-deficient anemia (IDA) from the anemia of chronic disease (ACD) and the combined state of ACD/IDA. Serum hepcidin-25 might be a marker resolving this problem. We investigated the extent to which serum hepcidin-25 enables the differentiation of the states above in comparison with the ferritin index plot, the so-called Thomas plot [soluble transferrin receptor (sTfR)/log ferritin and the reticulocyte hemoglobin content (CHr)]. Serum hepcidin-25 was determined in 155 anemic patients who were classified as having latent iron deficiency (latent ID), IDA, ACD, or ACD/IDA using the ferritin index plot (Thomas plot). Hepcidin-25 was determined using an isotope-dilution micro-HPLC-tandem mass spectrometry method. The ability to discriminate among these states based on serum hepcidin-25 alone or in combination with the CHr was evaluated in a receiver operating characteristic curve analysis and a comparison with the recently established ferritin index plot. Serum hepcidin-25 correlated with ferritin and the ferritin index. Use of a hepcidin-25 cutoff level of ≤4 nmol/l allowed the differentiation of IDA from ACD and ACD/IDA. Furthermore, the discrimination of ACD/IDA from ACD required combination with CHr in a new plot (hepcidin-25 and the CHr). The hepcidin-25 plot and the ferritin index plot showed a good correspondence in the differentiation of iron states in patients with anemia. Patients with IDA can be differentiated from ACD and ACD/IDA but not ACD from ACD/IDA based on hepcidin-25 alone. The combination of hepcidin-25 with CHr in the hepcidin-25 plot was useful for the differentiation of the states above. © 2010 Blackwell Publishing Ltd.

A study of the kinetics of isothermal nicotine desorption from silicon dioxide

NASA Astrophysics Data System (ADS)

Adnadjevic, Borivoj; Lazarevic, Natasa; Jovanovic, Jelena

2010-12-01

The isothermal kinetics of nicotine desorption from silicon dioxide (SiO 2) was investigated. The isothermal thermogravimetric curves of nicotine at temperatures of 115 °C, 130 °C and 152 °C were recorded. The kinetic parameters ( Ea, ln A) of desorption of nicotine were calculated using various methods (stationary point, model constants and differential isoconversion method). By applying the "model-fitting" method, it was found that the kinetic model of nicotine desorption from silicon dioxide was a phase boundary controlled reaction (contracting volume). The values of the kinetic parameters, Ea,α and ln Aα, complexly change with changing degree of desorption and a compensation effect exists. A new mechanism of activation for the desorption of the absorbed molecules of nicotine was suggested in agreement with model of selective energy transfer.

Kinetic Description of the Impedance Probe

NASA Astrophysics Data System (ADS)

Oberrath, Jens; Lapke, Martin; Mussenbrock, Thomas; Brinkmann, Ralf

2011-10-01

Active plasma resonance spectroscopy is a well known diagnostic method. Many concepts of this method are theoretically investigated and realized as a diagnostic tool, one of which is the impedance probe (IP). The application of such a probe in plasmas with pressures of a few Pa raises the question whether kinetic effects have to be taken into account or not. To address this question a kinetic model is necessary. A general kinetic model for an electrostatic concept of active plasma spectroscopy was presented by R.P. Brinkmann and can be used to describe the multipole resonance probe (MRP). In principle the IP is interpretable as a special case of the MRP in lower order. Thus, we are able to describe the IP by the kinetic model of the MRP. Based on this model we derive a solution to investigate the influence of kinetic effects to the resonance behavior of the IP. Active plasma resonance spectroscopy is a well known diagnostic method. Many concepts of this method are theoretically investigated and realized as a diagnostic tool, one of which is the impedance probe (IP). The application of such a probe in plasmas with pressures of a few Pa raises the question whether kinetic effects have to be taken into account or not. To address this question a kinetic model is necessary. A general kinetic model for an electrostatic concept of active plasma spectroscopy was presented by R.P. Brinkmann and can be used to describe the multipole resonance probe (MRP). In principle the IP is interpretable as a special case of the MRP in lower order. Thus, we are able to describe the IP by the kinetic model of the MRP. Based on this model we derive a solution to investigate the influence of kinetic effects to the resonance behavior of the IP. The authors acknowledge the support by the Deutsche Forschungsgemeinschaft (DFG) via the Ruhr University Research School and the Federal Ministry of Education and Research in frame of the PluTO project.

New User-Friendly Approach to Obtain an Eisenberg Plot and Its Use as a Practical Tool in Protein Sequence Analysis

PubMed Central

Keller, Rob C.A.

2011-01-01

The Eisenberg plot or hydrophobic moment plot methodology is one of the most frequently used methods of bioinformatics. Bioinformatics is more and more recognized as a helpful tool in Life Sciences in general, and recent developments in approaches recognizing lipid binding regions in proteins are promising in this respect. In this study a bioinformatics approach specialized in identifying lipid binding helical regions in proteins was used to obtain an Eisenberg plot. The validity of the Heliquest generated hydrophobic moment plot was checked and exemplified. This study indicates that the Eisenberg plot methodology can be transferred to another hydrophobicity scale and renders a user-friendly approach which can be utilized in routine checks in protein–lipid interaction and in protein and peptide lipid binding characterization studies. A combined approach seems to be advantageous and results in a powerful tool in the search of helical lipid-binding regions in proteins and peptides. The strength and limitations of the Eisenberg plot approach itself are discussed as well. The presented approach not only leads to a better understanding of the nature of the protein–lipid interactions but also provides a user-friendly tool for the search of lipid-binding regions in proteins and peptides. PMID:22016610

New user-friendly approach to obtain an Eisenberg plot and its use as a practical tool in protein sequence analysis.

PubMed

Keller, Rob C A

2011-01-01

The Eisenberg plot or hydrophobic moment plot methodology is one of the most frequently used methods of bioinformatics. Bioinformatics is more and more recognized as a helpful tool in Life Sciences in general, and recent developments in approaches recognizing lipid binding regions in proteins are promising in this respect. In this study a bioinformatics approach specialized in identifying lipid binding helical regions in proteins was used to obtain an Eisenberg plot. The validity of the Heliquest generated hydrophobic moment plot was checked and exemplified. This study indicates that the Eisenberg plot methodology can be transferred to another hydrophobicity scale and renders a user-friendly approach which can be utilized in routine checks in protein-lipid interaction and in protein and peptide lipid binding characterization studies. A combined approach seems to be advantageous and results in a powerful tool in the search of helical lipid-binding regions in proteins and peptides. The strength and limitations of the Eisenberg plot approach itself are discussed as well. The presented approach not only leads to a better understanding of the nature of the protein-lipid interactions but also provides a user-friendly tool for the search of lipid-binding regions in proteins and peptides.

Optimization of a direct spectrophotometric method to investigate the kinetics and inhibition of sialidases

PubMed Central

2012-01-01

Backgrounds Streptococcus pneumoniae expresses three distinct sialidases, NanA, NanB, and NanC, that are believed to be key virulence factors and thus, potential important drug targets. We previously reported that the three enzymes release different products from sialosides, but could share a common catalytic mechanism before the final step of product formation. However, the kinetic investigations of the three sialidases have not been systematically done thus far, due to the lack of an easy and steady measurement of sialidase reaction rate. Results In this work, we present further kinetic characterization of pneumococcal sialidases by using a direct spectrophotometric method with the chromogenic substrate p-nitrophenyl-N-acetylneuraminic acid (p-NP-Neu5Ac). Using our assay, the measured kinetic parameters of the three purified pneumococcal sialidase, NanA, NanB and NanC, were obtained and were in perfect agreement with the previously published data. The major advantage of this alternative method resides in the direct measurement of the released product, allowing to readily determine of initial reaction rates and record complete hydrolysis time courses. Conclusion We developed an accurate, fast and sensitive spectrophotometric method to investigate the kinetics of sialidase-catalyzed reactions. This fast, sensitive, inexpensive and accurate method could benefit the study of the kinetics and inhibition of sialidases in general. PMID:23031230

Specifying the Probability Characteristics of Funnel Plot Control Limits: An Investigation of Three Approaches

PubMed Central

Manktelow, Bradley N.; Seaton, Sarah E.

2012-01-01

Background Emphasis is increasingly being placed on the monitoring and comparison of clinical outcomes between healthcare providers. Funnel plots have become a standard graphical methodology to identify outliers and comprise plotting an outcome summary statistic from each provider against a specified ‘target’ together with upper and lower control limits. With discrete probability distributions it is not possible to specify the exact probability that an observation from an ‘in-control’ provider will fall outside the control limits. However, general probability characteristics can be set and specified using interpolation methods. Guidelines recommend that providers falling outside such control limits should be investigated, potentially with significant consequences, so it is important that the properties of the limits are understood. Methods Control limits for funnel plots for the Standardised Mortality Ratio (SMR) based on the Poisson distribution were calculated using three proposed interpolation methods and the probability calculated of an ‘in-control’ provider falling outside of the limits. Examples using published data were shown to demonstrate the potential differences in the identification of outliers. Results The first interpolation method ensured that the probability of an observation of an ‘in control’ provider falling outside either limit was always less than a specified nominal probability (p). The second method resulted in such an observation falling outside either limit with a probability that could be either greater or less than p, depending on the expected number of events. The third method led to a probability that was always greater than, or equal to, p. Conclusion The use of different interpolation methods can lead to differences in the identification of outliers. This is particularly important when the expected number of events is small. We recommend that users of these methods be aware of the differences, and specify which interpolation method is to be used prior to any analysis. PMID:23029202

Pseudo-second order models for the adsorption of safranin onto activated carbon: comparison of linear and non-linear regression methods.

PubMed

Kumar, K Vasanth

2007-04-02

Kinetic experiments were carried out for the sorption of safranin onto activated carbon particles. The kinetic data were fitted to pseudo-second order model of Ho, Sobkowsk and Czerwinski, Blanchard et al. and Ritchie by linear and non-linear regression methods. Non-linear method was found to be a better way of obtaining the parameters involved in the second order rate kinetic expressions. Both linear and non-linear regression showed that the Sobkowsk and Czerwinski and Ritchie's pseudo-second order models were the same. Non-linear regression analysis showed that both Blanchard et al. and Ho have similar ideas on the pseudo-second order model but with different assumptions. The best fit of experimental data in Ho's pseudo-second order expression by linear and non-linear regression method showed that Ho pseudo-second order model was a better kinetic expression when compared to other pseudo-second order kinetic expressions.

Lactate threshold by muscle electrical impedance in professional rowers

NASA Astrophysics Data System (ADS)

Jotta, B.; Coutinho, A. B. B.; Pino, A. V.; Souza, M. N.

2017-04-01

Lactate threshold (LT) is one of the physiological parameters usually used in rowing sport training prescription because it indicates the transitions from aerobic to anaerobic metabolism. Assessment of LT is classically based on a series of values of blood lactate concentrations obtained during progressive exercise tests and thus has an invasive aspect. The feasibility of noninvasive LT estimative through bioelectrical impedance spectroscopy (BIS) data collected in thigh muscles during rowing ergometer exercise tests was investigated. Nineteen professional rowers, age 19 (mean) ± 4.8 (standard deviation) yr, height 187.3 ± 6.6 cm, body mass 83 ± 7.7 kg, and training experience of 7 ± 4 yr, were evaluated in a rowing ergometer progressive test with paired measures of blood lactate concentration and BIS in thigh muscles. Bioelectrical impedance data were obtained by using a bipolar method of spectroscopy based on the current response to a voltage step. An electrical model was used to interpret BIS data and to derive parameters that were investigated to estimate LT noninvasively. From the serial blood lactate measurements, LT was also determined through Dmax method (LTDmax). The zero crossing of the second derivative of kinetic of the capacitance electrode (Ce), one of the BIS parameters, was used to estimate LT. The agreement between the LT estimates through BIS (LTBIS) and through Dmax method (LTDmax) was evaluated using Bland-Altman plots, leading to a mean difference between the estimates of just 0.07 W and a Pearson correlation coefficient r = 0.85. This result supports the utilization of the proposed method based on BIS parameters for estimating noninvasively the lactate threshold in rowing.

A new graphic method for estimation of distribution volume in chronic ischemic brain lesions on I-123 IMP SPECT; in prediction of regional CBF increase by bypass surgery

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

Odano, I.; Ohkubo, M.; Takahashi, N.

1994-05-01

The estimate the distribution volume (Vd) of Iodine-123 IMP brain SPECT, we developed a new graphic plot, the rate constant square method, which was useful to predict an increase of rCBF in the ischemic lesions caused by bypass surgery. The tracer kinetics of IMP was assumed to be a 2-compartment model as follows: dCb(t)/dt=K1Ca(t)-k2Cb(t), where K1 is rCBF(ml/g/min), k2 is the washout constant(/min), and K1/k2 is defined as distribution volume (Vd:ml/g). When input function Ca(t) is prepared, we can determine the relationship between K1, Delayed/Early ratio and Vd on the graph. The method was applied to 13 patients with chronicmore » cerebral infarction. Regional CBF was measured by the microsphere model and early and delayed scans were performed. In the normal area, K1 and Delayed/Early ratio were 0.5 ml/g/min and 1.0, respectively, then Vd (=31.5 ml/g) was obtained on the graph. 30.0 ml/g, the value in the infarct area was reduced. After bypass surgery undertaken on five patients, we observed a significant relationship between % increase of rCBF in the lesions and values of Vd. Since Vd reflects the extent of IMP retention in the brain tissue, we can predict an increase of rCBF by the bypass operation using this method.« less

Computer user's manual for a generalized curve fit and plotting program

NASA Technical Reports Server (NTRS)

Schlagheck, R. A.; Beadle, B. D., II; Dolerhie, B. D., Jr.; Owen, J. W.

1973-01-01

A FORTRAN coded program has been developed for generating plotted output graphs on 8-1/2 by 11-inch paper. The program is designed to be used by engineers, scientists, and non-programming personnel on any IBM 1130 system that includes a 1627 plotter. The program has been written to provide a fast and efficient method of displaying plotted data without having to generate any additions. Various output options are available to the program user for displaying data in four different types of formatted plots. These options include discrete linear, continuous, and histogram graphical outputs. The manual contains information about the use and operation of this program. A mathematical description of the least squares goodness of fit test is presented. A program listing is also included.

A method for developing design diagrams for ceramic and glass materials using fatigue data

NASA Technical Reports Server (NTRS)

Heslin, T. M.; Magida, M. B.; Forrest, K. A.

1986-01-01

The service lifetime of glass and ceramic materials can be expressed as a plot of time-to-failure versus applied stress whose plot is parametric in percent probability of failure. This type of plot is called a design diagram. Confidence interval estimates for such plots depend on the type of test that is used to generate the data, on assumptions made concerning the statistical distribution of the test results, and on the type of analysis used. This report outlines the development of design diagrams for glass and ceramic materials in engineering terms using static or dynamic fatigue tests, assuming either no particular statistical distribution of test results or a Weibull distribution and using either median value or homologous ratio analysis of the test results.

External Threat Risk Assessment Algorithm (ExTRAA)

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

Powell, Troy C.

Two risk assessment algorithms and philosophies have been augmented and combined to form a new algorit hm, the External Threat Risk Assessment Algorithm (ExTRAA), that allows for effective and statistically sound analysis of external threat sources in relation to individual attack methods . In addition to the attack method use probability and the attack method employment consequence, t he concept of defining threat sources is added to the risk assessment process. Sample data is tabulated and depicted in radar plots and bar graphs for algorithm demonstration purposes. The largest success of ExTRAA is its ability to visualize the kind ofmore » r isk posed in a given situation using the radar plot method.« less

The Rectangle Target Plot: A New Approach to the Graphical Presentation of Accuracy of Systems for Self-Monitoring of Blood Glucose.

PubMed

Stephan, Peter; Schmid, Christina; Freckmann, Guido; Pleus, Stefan; Haug, Cornelia; Müller, Peter

2015-10-09

The measurement accuracy of systems for self-monitoring of blood glucose (SMBG) is usually analyzed by a method comparison in which the analysis results are displayed using difference plots or similar graphs. However, such plots become difficult to comprehend as the number of data points displayed increases. This article introduces a new approach, the rectangle target plot (RTP), which aims to provide a simplified and comprehensible visualization of accuracy data. The RTP is based on ISO 15197 accuracy evaluations of SMBG systems. Two-sided tolerance intervals for normally distributed data are calculated for absolute and relative differences at glucose concentrations <100 mg/dL and ≥100 mg/dL. These tolerance intervals provide an estimator of where a 90% proportion of results is found with a confidence level of 95%. Plotting these tolerance intervals generates a rectangle whose center indicates the systematic measurement difference of the investigated system relative to the comparison method. The size of the rectangle depends on the measurement variability. The RTP provides a means of displaying measurement accuracy data in a simple and comprehensible manner. The visualization is simplified by reducing the displayed information from typically 200 data points to just 1 rectangle. Furthermore, this allows data for several systems or several lots from 1 system to be displayed clearly and concisely in a single graph. © 2015 Diabetes Technology Society.

Andrographolide sodium bisulphite-induced inactivation of urease: inhibitory potency, kinetics and mechanism.

PubMed

Mo, Zhi-Zhun; Wang, Xiu-Fen; Zhang, Xie; Su, Ji-Yan; Chen, Hai-Ming; Liu, Yu-Hong; Zhang, Zhen-Biao; Xie, Jian-Hui; Su, Zi-Ren

2015-07-16

The inhibitory effect of andrographolide sodium bisulphite (ASB) on jack bean urease (JBU) and Helicobacter pylori urease (HPU) was performed to elucidate the inhibitory potency, kinetics and mechanism of inhibition in 20 mM phosphate buffer, pH 7.0, 2 mM EDTA, 25 °C. The ammonia formations, indicator of urease activity, were examined using modified spectrophotometric Berthelot (phenol-hypochlorite) method. The inhibitory effect of ASB was characterized with IC50 values. Lineweaver-Burk and Dixon plots for JBU inhibition of ASB was constructed from the kinetic data. SH-blocking reagents and competitive active site Ni2+ binding inhibitors were employed for mechanism study. Molecular docking technique was used to provide some information on binding conformations as well as confirm the inhibition mode. The IC50 of ASB against JBU and HPU was 3.28±0.13 mM and 3.17±0.34 mM, respectively. The inhibition proved to be competitive and concentration- dependent in a slow-binding progress. The rapid formation of initial ASB-JBU complex with an inhibition constant of Ki=2.86×10(-3) mM was followed by a slow isomerization into the final complex with an overall inhibition constant of Ki*=1.33×10(-4) mM. The protective experiment proved that the urease active site is involved in the binding of ASB. Thiol reagents (L-cysteine and dithiothreithol) strongly protect the enzyme from the loss of enzymatic activity, while boric acid and fluoride show weaker protection, indicating that the active-site sulfhydryl group of JBU was potentially involved in the blocking process. Moreover, inhibition of ASB proved to be reversible since ASB-inactivated JBU could be reactivated by dithiothreitol application. Molecular docking assay suggested that ASB made contacts with the important sulfhydryl group Cys-592 residue and restricted the mobility of the active-site flap. ASB was a competitive inhibitor targeting thiol groups of urease in a slow-binding manner both reversibly and concentration-dependently, serving as a promising urease inhibitor for the treatment of urease-related diseases.

Enzymatic Kinetic Properties of the Lactate Dehydrogenase Isoenzyme C4 of the Plateau Pika (Ochotona curzoniae)

PubMed Central

Wang, Yang; Wei, Lian; Wei, Dengbang; Li, Xiao; Xu, Lina; Wei, Linna

2016-01-01

Testis-specific lactate dehydrogenase (LDH-C4) is one of the lactate dehydrogenase (LDH) isozymes that catalyze the terminal reaction of pyruvate to lactate in the glycolytic pathway. LDH-C4 in mammals was previously thought to be expressed only in spermatozoa and testis and not in other tissues. Plateau pika (Ochotona curzoniae) belongs to the genus Ochotona of the Ochotonidea family. It is a hypoxia-tolerant species living in remote mountain areas at altitudes of 3000–5000 m above sea level on the Qinghai-Tibet Plateau. Surprisingly, Ldh-c is expressed not only in its testis and sperm, but also in somatic tissues of plateau pika. To shed light on the function of LDH-C4 in somatic cells, Ldh-a, Ldh-b, and Ldh-c of plateau pika were subcloned into bacterial expression vectors. The pure enzymes of Lactate Dehydrogenase A4 (LDH-A4), Lactate Dehydrogenase B4 (LDH-B4), and LDH-C4 were prepared by a series of expression and purification processes, and the three enzymes were identified by the method of sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) and native polyacrylamide gel electrophoresis (PAGE). The enzymatic kinetics properties of these enzymes were studied by Lineweaver-Burk double-reciprocal plots. The results showed the Michaelis constant (Km) of LDH-C4 for pyruvate and lactate was 0.052 and 4.934 mmol/L, respectively, with an approximate 90 times higher affinity of LDH-C4 for pyruvate than for lactate. At relatively high concentrations of lactate, the inhibition constant (Ki) of the LDH isoenzymes varied: LDH-A4 (Ki = 26.900 mmol/L), LDH-B4 (Ki = 23.800 mmol/L), and LDH-C4 (Ki = 65.500 mmol/L). These data suggest that inhibition of lactate by LDH-A4 and LDH-B4 were stronger than LDH-C4. In light of the enzymatic kinetics properties, we suggest that the plateau pika can reduce reliance on oxygen supply and enhance its adaptation to the hypoxic environments due to increased anaerobic glycolysis by LDH-C4. PMID:26751442

The relative importance of decomposition and transport mechanisms in accounting for C profiles

NASA Astrophysics Data System (ADS)

Guenet, B.; Eglin, T.; Vasilyeva, N.; Peylin, P.; Ciais, P.; Chenu, C.

2012-10-01

Soil is the major terrestrial reservoirs of carbon, and a substantial part of this carbon is stored in deep layers, typically deeper than 50 cm below the surface. Several studies underlined the quantitative importance of this deep Soil Organic Carbon (SOC) pool and models are needed to better understand this stock and its evolution under climate and land-uses changes. In this study, we test and compare 3 simple theoretical models of vertical transport for SOC against SOC profiles measurements from a long-term bare fallow experiment carried out by the Central-Chernozem State Natural Biosphere Reserve named after V.V. Alekhin, in the Kursk Region of Russia. The transport schemes tested are diffusion, advection or both diffusion and advection. They are coupled to two different formulations of soil carbon decomposition kinetics. The first formulation is a first order kinetics widely used in global SOC decomposition models; the second one links SOC decomposition rate to the amount of fresh organic matter, representing a "priming effect". Field data are from a set of three bare fallow plots where soil received no input during the past 20, 26 and 58 yr respectively. Parameters of the models were optimized using a Bayesian method. The best results are obtained when SOC decomposition is assumed to be controlled by fresh organic matter. In comparison to the first-order kinetic model, the "priming" model reduces the underestimation of SOC decomposition in the top layers and the over estimation in the deep layers. We also observe that the transport scheme that improved the fit with the data depends on the soil carbon mineralization formulation chosen. When soil carbon decomposition is modelled to depend on the fresh organic matter amount, the transport mechanisms which improves best the fit to the SOC profile data is the model representing both advection and diffusion. Interestingly, the older the bare fallow is, the lesser the need for diffusion is. This suggests that stabilized carbon may not be transported within the profile by the same mechanisms than more labile carbon.

Nearest neighbor imputation of species-level, plot-scale forest structure attributes from LiDAR data

Treesearch

Andrew T. Hudak; Nicholas L. Crookston; Jeffrey S. Evans; David E. Hall; Michael J. Falkowski

2008-01-01

Meaningful relationships between forest structure attributes measured in representative field plots on the ground and remotely sensed data measured comprehensively across the same forested landscape facilitate the production of maps of forest attributes such as basal area (BA) and tree density (TD). Because imputation methods can efficiently predict multiple response...

SOIL-AIR PERMEABILITY MEASUREMENT WITH A TRANSIENT PRESSURE BUILDUP METHOD

EPA Science Inventory

An analytical solution for transient pressure change in a single venting well was derived from mass conservation of air, Darcy's law of flow in porous media, and the ideal gas law equation of state. Slopes of plots of Pw2 against ln (t+Δt)/Δt similar to Homer's plot were used to ...

Detection of the fracture zone by the method of recurrence plot

NASA Astrophysics Data System (ADS)

Hilarov, V. L.

2017-12-01

Recurrence plots (RPs) and recurrence quantification analysis (RQA) characteristics for the normal component of the displacement vector upon excitation of a defect steel plate by a sound pulse are analyzed. Different cases of spatial distribution of defects (uniform and normal) are considered, and a difference in the RQA parameters in these cases is revealed.

Braconid wasp (Hymenoptera: Braconidae) diversity in forest plots under different silvicultural methods

Treesearch

C.N. Lewis; J.B. Whitfield

1999-01-01

Braconid wasps were used as an indicator group to test the hypothesis that the degree of disturbance in silvicultural treatments will change the total abundance and composition of species. Wasps were collected with Malaise traps on undisturbed (control), moderately disturbed (pine single-tree selection) and highly disturbed (pine-hardwood seed-tree) research plots of...

Survivability Versus Time

NASA Technical Reports Server (NTRS)

Joyner, James J., Sr.

2014-01-01

Develop Survivability vs Time Model as a decision-evaluation tool to assess various emergency egress methods used at Launch Complex 39B (LC 39B) and in the Vehicle Assembly Building (VAB) on NASAs Kennedy Space Center. For each hazard scenario, develop probability distributions to address statistical uncertainty resulting in survivability plots over time and composite survivability plots encompassing multiple hazard scenarios.