Efficient reactive Brownian dynamics

DOE PAGES

Donev, Aleksandar; Yang, Chiao-Yu; Kim, Changho

2018-01-21

We develop a Split Reactive Brownian Dynamics (SRBD) algorithm for particle simulations of reaction-diffusion systems based on the Doi or volume reactivity model, in which pairs of particles react with a specified Poisson rate if they are closer than a chosen reactive distance. In our Doi model, we ensure that the microscopic reaction rules for various association and dissociation reactions are consistent with detailed balance (time reversibility) at thermodynamic equilibrium. The SRBD algorithm uses Strang splitting in time to separate reaction and diffusion and solves both the diffusion-only and reaction-only subproblems exactly, even at high packing densities. To efficiently processmore » reactions without uncontrolled approximations, SRBD employs an event-driven algorithm that processes reactions in a time-ordered sequence over the duration of the time step. A grid of cells with size larger than all of the reactive distances is used to schedule and process the reactions, but unlike traditional grid-based methods such as reaction-diffusion master equation algorithms, the results of SRBD are statistically independent of the size of the grid used to accelerate the processing of reactions. We use the SRBD algorithm to compute the effective macroscopic reaction rate for both reaction-limited and diffusion-limited irreversible association in three dimensions and compare to existing theoretical predictions at low and moderate densities. We also study long-time tails in the time correlation functions for reversible association at thermodynamic equilibrium and compare to recent theoretical predictions. Finally, we compare different particle and continuum methods on a model exhibiting a Turing-like instability and pattern formation. Our studies reinforce the common finding that microscopic mechanisms and correlations matter for diffusion-limited systems, making continuum and even mesoscopic modeling of such systems difficult or impossible. We also find that for models in which particles diffuse off lattice, such as the Doi model, reactions lead to a spurious enhancement of the effective diffusion coefficients.« less

Efficient reactive Brownian dynamics

NASA Astrophysics Data System (ADS)

Donev, Aleksandar; Yang, Chiao-Yu; Kim, Changho

2018-01-01

We develop a Split Reactive Brownian Dynamics (SRBD) algorithm for particle simulations of reaction-diffusion systems based on the Doi or volume reactivity model, in which pairs of particles react with a specified Poisson rate if they are closer than a chosen reactive distance. In our Doi model, we ensure that the microscopic reaction rules for various association and dissociation reactions are consistent with detailed balance (time reversibility) at thermodynamic equilibrium. The SRBD algorithm uses Strang splitting in time to separate reaction and diffusion and solves both the diffusion-only and reaction-only subproblems exactly, even at high packing densities. To efficiently process reactions without uncontrolled approximations, SRBD employs an event-driven algorithm that processes reactions in a time-ordered sequence over the duration of the time step. A grid of cells with size larger than all of the reactive distances is used to schedule and process the reactions, but unlike traditional grid-based methods such as reaction-diffusion master equation algorithms, the results of SRBD are statistically independent of the size of the grid used to accelerate the processing of reactions. We use the SRBD algorithm to compute the effective macroscopic reaction rate for both reaction-limited and diffusion-limited irreversible association in three dimensions and compare to existing theoretical predictions at low and moderate densities. We also study long-time tails in the time correlation functions for reversible association at thermodynamic equilibrium and compare to recent theoretical predictions. Finally, we compare different particle and continuum methods on a model exhibiting a Turing-like instability and pattern formation. Our studies reinforce the common finding that microscopic mechanisms and correlations matter for diffusion-limited systems, making continuum and even mesoscopic modeling of such systems difficult or impossible. We also find that for models in which particles diffuse off lattice, such as the Doi model, reactions lead to a spurious enhancement of the effective diffusion coefficients.

Efficient reactive Brownian dynamics

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

Donev, Aleksandar; Yang, Chiao-Yu; Kim, Changho

We develop a Split Reactive Brownian Dynamics (SRBD) algorithm for particle simulations of reaction-diffusion systems based on the Doi or volume reactivity model, in which pairs of particles react with a specified Poisson rate if they are closer than a chosen reactive distance. In our Doi model, we ensure that the microscopic reaction rules for various association and dissociation reactions are consistent with detailed balance (time reversibility) at thermodynamic equilibrium. The SRBD algorithm uses Strang splitting in time to separate reaction and diffusion and solves both the diffusion-only and reaction-only subproblems exactly, even at high packing densities. To efficiently processmore » reactions without uncontrolled approximations, SRBD employs an event-driven algorithm that processes reactions in a time-ordered sequence over the duration of the time step. A grid of cells with size larger than all of the reactive distances is used to schedule and process the reactions, but unlike traditional grid-based methods such as reaction-diffusion master equation algorithms, the results of SRBD are statistically independent of the size of the grid used to accelerate the processing of reactions. We use the SRBD algorithm to compute the effective macroscopic reaction rate for both reaction-limited and diffusion-limited irreversible association in three dimensions and compare to existing theoretical predictions at low and moderate densities. We also study long-time tails in the time correlation functions for reversible association at thermodynamic equilibrium and compare to recent theoretical predictions. Finally, we compare different particle and continuum methods on a model exhibiting a Turing-like instability and pattern formation. Our studies reinforce the common finding that microscopic mechanisms and correlations matter for diffusion-limited systems, making continuum and even mesoscopic modeling of such systems difficult or impossible. We also find that for models in which particles diffuse off lattice, such as the Doi model, reactions lead to a spurious enhancement of the effective diffusion coefficients.« less

MALDI MS-based Composition Analysis of the Polymerization Reaction of Toluene Diisocyanate (TDI) and Ethylene Glycol (EG).

PubMed

Ahn, Yeong Hee; Lee, Yeon Jung; Kim, Sung Ho

2015-01-01

This study describes an MS-based analysis method for monitoring changes in polymer composition during the polyaddition polymerization reaction of toluene diisocyanate (TDI) and ethylene glycol (EG). The polymerization was monitored as a function of reaction time using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI TOF MS). The resulting series of polymer adducts terminated with various end-functional groups were precisely identified and the relative compositions of those series were estimated. A new MALDI MS data interpretation method was developed, consisting of a peak-resolving algorithm for overlapping peaks in MALDI MS spectra, a retrosynthetic analysis for the generation of reduced unit mass peaks, and a Gaussian fit-based selection of the most prominent polymer series among the reconstructed unit mass peaks. This method of data interpretation avoids errors originating from side reactions due to the presence of trace water in the reaction mixture or MALDI analysis. Quantitative changes in the relative compositions of the resulting polymer products were monitored as a function of reaction time. These results demonstrate that the mass data interpretation method described herein can be a powerful tool for estimating quantitative changes in the compositions of polymer products arising during a polymerization reaction.

Psy Toolkit: A Novel Web-Based Method for Running Online Questionnaires and Reaction-Time Experiments

ERIC Educational Resources Information Center

Stoet, Gijsbert

2017-01-01

This article reviews PsyToolkit, a free web-based service designed for setting up, running, and analyzing online questionnaires and reaction-time (RT) experiments. It comes with extensive documentation, videos, lessons, and libraries of free-to-use psychological scales and RT experiments. It provides an elaborate interactive environment to use (or…

Synthesis of Cesium Lead Halide Perovskite Nanocrystals in a Droplet-Based Microfluidic Platform: Fast Parametric Space Mapping.

PubMed

Lignos, Ioannis; Stavrakis, Stavros; Nedelcu, Georgian; Protesescu, Loredana; deMello, Andrew J; Kovalenko, Maksym V

2016-03-09

Prior to this work, fully inorganic nanocrystals of cesium lead halide perovskite (CsPbX3, X = Br, I, Cl and Cl/Br and Br/I mixed halide systems), exhibiting bright and tunable photoluminescence, have been synthesized using conventional batch (flask-based) reactions. Unfortunately, our understanding of the parameters governing the formation of these nanocrystals is still very limited due to extremely fast reaction kinetics and multiple variables involved in ion-metathesis-based synthesis of such multinary halide systems. Herein, we report the use of a droplet-based microfluidic platform for the synthesis of CsPbX3 nanocrystals. The combination of online photoluminescence and absorption measurements and the fast mixing of reagents within such a platform allows the rigorous and rapid mapping of the reaction parameters, including molar ratios of Cs, Pb, and halide precursors, reaction temperatures, and reaction times. This translates into enormous savings in reagent usage and screening times when compared to analogous batch synthetic approaches. The early-stage insight into the mechanism of nucleation of metal halide nanocrystals suggests similarities with multinary metal chalcogenide systems, albeit with much faster reaction kinetics in the case of halides. Furthermore, we show that microfluidics-optimized synthesis parameters are also directly transferrable to the conventional flask-based reaction.

Investigation to biodiesel production by the two-step homogeneous base-catalyzed transesterification.

PubMed

Ye, Jianchu; Tu, Song; Sha, Yong

2010-10-01

For the two-step transesterification biodiesel production made from the sunflower oil, based on the kinetics model of the homogeneous base-catalyzed transesterification and the liquid-liquid phase equilibrium of the transesterification product, the total methanol/oil mole ratio, the total reaction time, and the split ratios of methanol and reaction time between the two reactors in the stage of the two-step reaction are determined quantitatively. In consideration of the transesterification intermediate product, both the traditional distillation separation process and the improved separation process of the two-step reaction product are investigated in detail by means of the rigorous process simulation. In comparison with the traditional distillation process, the improved separation process of the two-step reaction product has distinct advantage in the energy duty and equipment requirement due to replacement of the costly methanol-biodiesel distillation column. Copyright 2010 Elsevier Ltd. All rights reserved.

Donders revisited: Discrete or continuous temporal processing underlying reaction time distributions?

PubMed

Bao, Yan; Yang, Taoxi; Lin, Xiaoxiong; Pöppel, Ernst

2016-09-01

Differences of reaction times to specific stimulus configurations are used as indicators of cognitive processing stages. In this classical experimental paradigm, continuous temporal processing is implicitly assumed. Multimodal response distributions indicate, however, discrete time sampling, which is often masked by experimental conditions. Differences in reaction times reflect discrete temporal mechanisms that are pre-semantically implemented and suggested to be based on entrained neural oscillations. © 2016 The Institute of Psychology, Chinese Academy of Sciences and John Wiley & Sons Australia, Ltd.

The Fixed-Links Model in Combination with the Polynomial Function as a Tool for Investigating Choice Reaction Time Data

ERIC Educational Resources Information Center

Schweizer, Karl

2006-01-01

A model with fixed relations between manifest and latent variables is presented for investigating choice reaction time data. The numbers for fixation originate from the polynomial function. Two options are considered: the component-based (1 latent variable for each component of the polynomial function) and composite-based options (1 latent…

Use of virtual reality intervention to improve reaction time in children with cerebral palsy: A randomized controlled trial.

PubMed

Pourazar, Morteza; Mirakhori, Fatemeh; Hemayattalab, Rasool; Bagherzadeh, Fazlolah

2017-09-21

The purpose of this study was to investigate the training effects of Virtual Reality (VR) intervention program on reaction time in children with cerebral palsy. Thirty boys ranging from 7 to 12 years (mean = 11.20; SD = .76) were selected by available sampling method and randomly divided into the experimental and control groups. Simple Reaction Time (SRT) and Discriminative Reaction Time (DRT) were measured at baseline and 1 day after completion of VR intervention. Multivariate analysis of variance (MANOVA) and paired sample t-test were performed to analyze the results. MANOVA test revealed significant effects for group in posttest phase, with lower reaction time in both measures for the experimental group. Based on paired sample t-test results, both RT measures significantly improved in experimental group following the VR intervention program. This paper proposes VR as a promising tool into the rehabilitation process for improving reaction time in children with cerebral palsy.

Synthesis biolubricant from rubber seed oil

NASA Astrophysics Data System (ADS)

Hung, Nguyen Tran Dong; Tuyen, Dang Thi Hong; Viet, Tran Tan

2017-09-01

The objective was biolubricant preparation from rubber seed oil (RSO) using polymerization reactor with/without catalyst in batch reactor. Before become reactant in polymerization reaction, a non-edible rubber seed oil was converted into methyl ester by esterification/tranesterification reaction with methanol and acid/base catalyst. The polymerization reaction parameters investigated were reaction time, temperature and weight ratio (catalyst with feed), and their effect on the bio lubricant formation. The result show significant conversion of methyl ester to bio lubricant in the temperature reaction of 160°C, reaction time of 2h min and ratio of super acid catalyst (tetrafluoroboric acid-sHBF4) of 3 %w/w. The resulting products were confirmed by GC-MS, FTIR spectroscopy and also analyzed for the viscosity. The best viscosity value of RSOFAME polymer was 110.6 cSt when the condition polymerization reaction were 160 °C, reaction time 3h, 6 wt% mass ratio of oil:catalyst.

Influence of reaction condition on viscosity of polyurethane modified epoxy based on glycerol monooleate

NASA Astrophysics Data System (ADS)

Triwulandari, Evi; Ramadhan, Mohammad Kemilau; Ghozali, Muhammad

2017-01-01

Polyurethane modified epoxy based on glycerol monooleate (PME-GMO) was synthesized. GMO as polyol for synthesis of PME-GMO was synthesized via Fisher Esterification between oleic acid from palm oil and glycerol by using sulfuric acid as catalyst with time variation i.e. 3, 4, 5 and 6 hours at 160°C. Characterizations of GMO were carried out by analysis of acid number, hydroxyl value and FTIR. The data show that the conversion of oleic acid to ester compound is directly proportional with the increasing of reaction time but the enhancement is not significant after 3 hours. Furthermore, GMO product was used as polyol for modification of epoxy with polyurethane. Modification of epoxy with polyurethane was performed by reacted epoxy, tolonate and GMO simultaneously in one step. In this research, the reaction condition was varied i.e. time reaction (0.5; 1; 1.5; 2; 2.5 hours), composition of polyurethane used (10%, 20% toward epoxy) and rasio of tolonate and GMO (NCO/OH ratio) as component of polyurethane (1.5 and 2.5). Characterization of polyurethane modified epoxy based on glycerol (PME-GMO) was conducted by viscosity and FTIR analysis. The viscosity of PME-GMO increased with increasing of reaction time, polyurethane composition and NCO/OH ratio.

The Impact of a Rigorous Multiple Work Shift Schedule and Day Versus Night Shift Work on Reaction Time and Balance Performance in Female Nurses: A Repeated Measures Study.

PubMed

Thompson, Brennan J; Stock, Matt S; Banuelas, Victoria K; Akalonu, Chibuzo C

2016-07-01

The aim of this study was to determine the impact of a demanding work schedule involving long, cumulative work shifts on response time and balance-related performance outcomes and to evaluate the prevalence of musculoskeletal disorders between day and night shift working nurses. A questionnaire was used to identify the prevalence of past (12-month) and current (7-day) musculoskeletal disorders. Nurses worked three 12-hour work shifts in a 4-day period. Reaction time and balance tests were conducted before and after the work period. The work period induced impairments for reaction time, errors on reaction time tasks, and balance performance, independent of shift type. Musculoskeletal symptom prevalence was high in workers of both work shifts. Compressed work shifts caused performance-based fatigue in nurses. Reaction time and balance tests may be sensitive fatigue identification markers in nurses.

Anomalous dielectric relaxation with linear reaction dynamics in space-dependent force fields.

PubMed

Hong, Tao; Tang, Zhengming; Zhu, Huacheng

2016-12-28

The anomalous dielectric relaxation of disordered reaction with linear reaction dynamics is studied via the continuous time random walk model in the presence of space-dependent electric field. Two kinds of modified reaction-subdiffusion equations are derived for different linear reaction processes by the master equation, including the instantaneous annihilation reaction and the noninstantaneous annihilation reaction. If a constant proportion of walkers is added or removed instantaneously at the end of each step, there will be a modified reaction-subdiffusion equation with a fractional order temporal derivative operating on both the standard diffusion term and a linear reaction kinetics term. If the walkers are added or removed at a constant per capita rate during the waiting time between steps, there will be a standard linear reaction kinetics term but a fractional order temporal derivative operating on an anomalous diffusion term. The dielectric polarization is analyzed based on the Legendre polynomials and the dielectric properties of both reactions can be expressed by the effective rotational diffusion function and component concentration function, which is similar to the standard reaction-diffusion process. The results show that the effective permittivity can be used to describe the dielectric properties in these reactions if the chemical reaction time is much longer than the relaxation time.

Polymerization-based signal amplification under ambient conditions with thirty-five second reaction times.

PubMed

Kaastrup, Kaja; Sikes, Hadley D

2012-10-21

Although polymerization-based amplification (PBA) has demonstrated promise as an inexpensive technique for use in molecular diagnostics, oxygen inhibition of radical photopolymerization has hindered its implementation in point-of-care devices. The addition of 0.3-0.7 μM eosin to an aqueous acrylate monomer solution containing a tertiary amine allows an interfacial polymerization reaction to proceed in air only near regions of a test surface where additional eosin initiators coupled to proteins have been localized as a function of molecular recognition events. The dose of light required for the reaction is inversely related to eosin concentration. This system achieves sensitivities comparable to those reported for inert gas-purged systems and requires significantly shorter reaction times. We provide several comparisons of this system with other implementations of polymerization-based amplification.

Exposure-time based modeling of nonlinear reactive transport in porous media subject to physical and geochemical heterogeneity.

PubMed

Sanz-Prat, Alicia; Lu, Chuanhe; Amos, Richard T; Finkel, Michael; Blowes, David W; Cirpka, Olaf A

2016-09-01

Transport of reactive solutes in groundwater is affected by physical and chemical heterogeneity of the porous medium, leading to complex spatio-temporal patterns of concentrations and reaction rates. For certain cases of bioreactive transport, it could be shown that the concentrations of reactive constituents in multi-dimensional domains are approximately aligned with isochrones, that is, lines of identical travel time, provided that the chemical properties of the matrix are uniform. We extend this concept to combined physical and chemical heterogeneity by additionally considering the time that a water parcel has been exposed to reactive materials, the so-called exposure time. We simulate bioreactive transport in a one-dimensional domain as function of time and exposure time, rather than space. Subsequently, we map the concentrations to multi-dimensional heterogeneous domains by means of the mean exposure time at each location in the multi-dimensional domain. Differences in travel and exposure time at a given location are accounted for as time difference. This approximation simplifies reactive-transport simulations significantly under conditions of steady-state flow when reactions are restricted to specific locations. It is not expected to be exact in realistic applications because the underlying assumption, such as neglecting transverse mixing altogether, may not hold. We quantify the error introduced by the approximation for the hypothetical case of a two-dimensional, binary aquifer made of highly-permeable, non-reactive and low-permeable, reactive materials releasing dissolved organic matter acting as electron donor for aerobic respiration and denitrification. The kinetically controlled reactions are catalyzed by two non-competitive bacteria populations, enabling microbial growth. Even though the initial biomass concentrations were uniform, the interplay between transport, non-uniform electron-donor supply, and bio-reactions led to distinct spatial patterns of the two types of biomass at late times. Results obtained by mapping the exposure-time based results to the two-dimensional domain are compared with simulations based on the two-dimensional, spatially explicit advection-dispersion-reaction equation. Once quasi-steady state has been reached, we find a good agreement in terms of the chemical-compound concentrations between the two approaches inside the reactive zones, whereas the exposure-time based model is not able to capture reactions occurring in the zones with zero electron-donor release. We conclude that exposure-time models provide good approximations of nonlinear bio-reactive transport when transverse mixing is not the overall controlling process and all reactions are essentially restricted to distinct reactive zones. Copyright © 2016 Elsevier B.V. All rights reserved.

Accelerating rejection-based simulation of biochemical reactions with bounded acceptance probability

NASA Astrophysics Data System (ADS)

Thanh, Vo Hong; Priami, Corrado; Zunino, Roberto

2016-06-01

Stochastic simulation of large biochemical reaction networks is often computationally expensive due to the disparate reaction rates and high variability of population of chemical species. An approach to accelerate the simulation is to allow multiple reaction firings before performing update by assuming that reaction propensities are changing of a negligible amount during a time interval. Species with small population in the firings of fast reactions significantly affect both performance and accuracy of this simulation approach. It is even worse when these small population species are involved in a large number of reactions. We present in this paper a new approximate algorithm to cope with this problem. It is based on bounding the acceptance probability of a reaction selected by the exact rejection-based simulation algorithm, which employs propensity bounds of reactions and the rejection-based mechanism to select next reaction firings. The reaction is ensured to be selected to fire with an acceptance rate greater than a predefined probability in which the selection becomes exact if the probability is set to one. Our new algorithm improves the computational cost for selecting the next reaction firing and reduces the updating the propensities of reactions.

Accelerating rejection-based simulation of biochemical reactions with bounded acceptance probability

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

Thanh, Vo Hong, E-mail: vo@cosbi.eu; Priami, Corrado, E-mail: priami@cosbi.eu; Department of Mathematics, University of Trento, Trento

Stochastic simulation of large biochemical reaction networks is often computationally expensive due to the disparate reaction rates and high variability of population of chemical species. An approach to accelerate the simulation is to allow multiple reaction firings before performing update by assuming that reaction propensities are changing of a negligible amount during a time interval. Species with small population in the firings of fast reactions significantly affect both performance and accuracy of this simulation approach. It is even worse when these small population species are involved in a large number of reactions. We present in this paper a new approximatemore » algorithm to cope with this problem. It is based on bounding the acceptance probability of a reaction selected by the exact rejection-based simulation algorithm, which employs propensity bounds of reactions and the rejection-based mechanism to select next reaction firings. The reaction is ensured to be selected to fire with an acceptance rate greater than a predefined probability in which the selection becomes exact if the probability is set to one. Our new algorithm improves the computational cost for selecting the next reaction firing and reduces the updating the propensities of reactions.« less

Cold-Curing Structural Epoxy Resins: Analysis of the Curing Reaction as a Function of Curing Time and Thickness

PubMed Central

Esposito Corcione, Carola; Freuli, Fabrizio; Frigione, Mariaenrica

2014-01-01

The curing reaction of a commercial cold-curing structural epoxy resin, specifically formulated for civil engineering applications, was analyzed by thermal analysis as a function of the curing time and the sample thickness. Original and remarkable results regarding the effects of curing time on the glass transition temperature and on the residual heat of reaction of the cold-cured epoxy were obtained. The influence of the sample thickness on the curing reaction of the cold-cured resin was also deeply investigated. A highly exothermal reaction, based on a self-activated frontal polymerization reaction, was supposed and verified trough a suitable temperature signal acquisition system, specifically realized for this measurement. This is one of the first studies carried out on the curing behavior of these peculiar cold-cured epoxy resins as a function of curing time and thickness. PMID:28788215

Cold-Curing Structural Epoxy Resins: Analysis of the Curing Reaction as a Function of Curing Time and Thickness.

PubMed

Corcione, Carola Esposito; Freuli, Fabrizio; Frigione, Mariaenrica

2014-09-22

The curing reaction of a commercial cold-curing structural epoxy resin, specifically formulated for civil engineering applications, was analyzed by thermal analysis as a function of the curing time and the sample thickness. Original and remarkable results regarding the effects of curing time on the glass transition temperature and on the residual heat of reaction of the cold-cured epoxy were obtained. The influence of the sample thickness on the curing reaction of the cold-cured resin was also deeply investigated. A highly exothermal reaction, based on a self-activated frontal polymerization reaction, was supposed and verified trough a suitable temperature signal acquisition system, specifically realized for this measurement. This is one of the first studies carried out on the curing behavior of these peculiar cold-cured epoxy resins as a function of curing time and thickness.

Team-Based Learning's Effects on Standardized Test Scores and Student Reactions

ERIC Educational Resources Information Center

Ulrich, Deborah L.; Brewer, Tracy; Steele-Johnson, Deborah; Juvina, Ion; Peyton, Elizabeth; Hammond, Crystal

2017-01-01

We examined the effects of team-based learning (TBL) versus traditional and enhanced lecture-based instruction over time (Study 1; N = 532 nursing students) and the psychometric properties of the Team Based Learning Student Assessment Instrument (TBL-SAI), a popular measure of reactions to TBL (Study 2; N = 323 nursing and medical students).…

Reaction temperature sensing (RTS)-based control for Li-ion battery safety

PubMed Central

Zhang, Guangsheng; Cao, Lei; Ge, Shanhai; Wang, Chao-Yang; Shaffer, Christian E.; Rahn, Christopher D.

2015-01-01

We report reaction temperature sensing (RTS)-based control to fundamentally enhance Li-ion battery safety. RTS placed at the electrochemical interface inside a Li-ion cell is shown to detect temperature rise much faster and more accurately than external measurement of cell surface temperature. We demonstrate, for the first time, that RTS-based control shuts down a dangerous short-circuit event 3 times earlier than surface temperature- based control and prevents cell overheating by 50 °C and the resultant cell damage. PMID:26658957

Design Factors Affecting the Reaction Time for Identifying Toilet Signs: A Preliminary Study.

PubMed

Chen, Yi-Lang; Sie, Cai-Cin

2016-04-01

This study focused on the manner in which design factors affect the reaction time for identifying toilet signs. Taiwanese university students and staff members (50 men, 50 women; M age = 23.5 year, SD = 5.7) participated in the study. The 36 toilet signs were modified on three factors (six presenting styles, two figure-ground exchanges, and three colors), and the reaction time data of all participants were collected when the signs were presented in a simulation onscreen. Participants were quickest when reading Chinese text, followed by graphics and English texts. The findings also showed that men and women had different reaction times across various design combinations. These findings can serve as a reference for practically designing toilet signs, since design factors can lead to difficulties with comprehension based on reaction time measurements. © The Author(s) 2016.

Real-time monitoring of enzyme-free strand displacement cascades by colorimetric assays

NASA Astrophysics Data System (ADS)

Duan, Ruixue; Wang, Boya; Hong, Fan; Zhang, Tianchi; Jia, Yongmei; Huang, Jiayu; Hakeem, Abdul; Liu, Nannan; Lou, Xiaoding; Xia, Fan

2015-03-01

The enzyme-free toehold-mediated strand displacement reaction has shown potential for building programmable DNA circuits, biosensors, molecular machines and chemical reaction networks. Here we report a simple colorimetric method using gold nanoparticles as signal generators for the real-time detection of the product of the strand displacement cascade. During the process the assembled gold nanoparticles can be separated, resulting in a color change of the solution. This assay can also be applied in complex mixtures, fetal bovine serum, and to detect single-base mismatches. These results suggest that this method could be of general utility to monitor more complex enzyme-free strand displacement reaction-based programmable systems or for further low-cost diagnostic applications.The enzyme-free toehold-mediated strand displacement reaction has shown potential for building programmable DNA circuits, biosensors, molecular machines and chemical reaction networks. Here we report a simple colorimetric method using gold nanoparticles as signal generators for the real-time detection of the product of the strand displacement cascade. During the process the assembled gold nanoparticles can be separated, resulting in a color change of the solution. This assay can also be applied in complex mixtures, fetal bovine serum, and to detect single-base mismatches. These results suggest that this method could be of general utility to monitor more complex enzyme-free strand displacement reaction-based programmable systems or for further low-cost diagnostic applications. Electronic supplementary information (ESI) available: Experimental procedures and analytical data are provided. See DOI: 10.1039/c5nr00697j

Rule-Based Event Processing and Reaction Rules

NASA Astrophysics Data System (ADS)

Paschke, Adrian; Kozlenkov, Alexander

Reaction rules and event processing technologies play a key role in making business and IT / Internet infrastructures more agile and active. While event processing is concerned with detecting events from large event clouds or streams in almost real-time, reaction rules are concerned with the invocation of actions in response to events and actionable situations. They state the conditions under which actions must be taken. In the last decades various reaction rule and event processing approaches have been developed, which for the most part have been advanced separately. In this paper we survey reaction rule approaches and rule-based event processing systems and languages.

A new chitosan Schiff base supported Pd(II) complex for microwave-assisted synthesis of biaryls compounds

NASA Astrophysics Data System (ADS)

Baran, Talat

2017-08-01

In this study, a new heterogeneous palladium (II) catalyst that contains O-carboxymethyl chitosan Schiff base has been designed for Suzuki coupling reactions. The chemical structures of the synthesized catalyst were characterized with the FTIR, TG/DTG, ICP-OES, SEM/EDAX, 1H NMR, 13C NMR, GC/MS, XRD, and magnetic moment techniques. The reusability and catalytic behavior of heterogeneous catalyst was tested towards Suzuki reactions. As a result of the tests, excellent selectivity was obtained, and by-products of homo coupling were not seen in the spectra. The biaryls products were identified on a GC/MS. In addition, it was determined in the reusability tests that the catalysts could be used several times (seven runs). More importantly, with very low catalyst loading (6 × 10-3 mol %) in very short reaction time (5 min), chitosan Schiff base supported Pd(II) complex gave high TON and TOF values. These findings showed that Schiff base supported Pd(II) catalyst is suitable for Suzuki cross coupling reactions.

Systemic effect of mineral aggregate-based cements: histopathological analysis in rats.

PubMed

Garcia, Lucas da Fonseca Roberti; Huck, Claudia; Magalhães, Fernando Augusto Cintra; Souza, Pedro Paulo Chaves de; Souza Costa, Carlos Alberto de

2017-01-01

Several studies reported the local tissue reaction caused by mineral aggregate-based cements. However, few studies have investigated the systemic effects promoted by these cements on liver and kidney when directly applied to connective tissue. The purpose of this in vivo study was to investigate the systemic effect of mineral aggregate-based cements on the livers and kidneys of rats. Samples of Mineral Trioxide Aggregate (MTA) and a calcium aluminate-based cement (EndoBinder) containing different radiopacifiers were implanted into the dorsum of 40 rats. After 7 and 30 d, samples of subcutaneous, liver and kidney tissues were submitted to histopathological analysis. A score (0-3) was used to grade the inflammatory reaction. Blood samples were collected to evaluate changes in hepatic and renal functions of animals. The moderate inflammatory reaction (2) observed for 7 d in the subcutaneous tissue decreased with time for all cements. The thickness of inflammatory capsules also presented a significant decrease with time (P<.05). Systemically, all cements caused adverse inflammatory reactions in the liver and kidney, being more evident for MTA, persisting until the end of the analysis. Liver functions increased significantly for MTA during 30 d (P<.05). The different cements induced to a locally limited inflammatory reaction. However, from the systemic point of view, the cements promoted significant inflammatory reactions in the liver and kidney. For MTA, the reactions were more accentuated.

Progression in High School Students' (Aged 16-18) Conceptualizations about Chemical Reactions in Solution.

ERIC Educational Resources Information Center

Boo, Hong-Kwen; Watson, J. R.

2001-01-01

Explores the development over time of students' understandings of the concept of chemical reaction in the context of two familiar reactions in solution. Based on interviews (n=48), results show that students made some progress in their understanding of the concept of chemical reaction but some fundamental misconceptions remained. (Author/MM)

Reaction time as an indicator of insufficient effort: Development and validation of an embedded performance validity parameter.

PubMed

Stevens, Andreas; Bahlo, Simone; Licha, Christina; Liske, Benjamin; Vossler-Thies, Elisabeth

2016-11-30

Subnormal performance in attention tasks may result from various sources including lack of effort. In this report, the derivation and validation of a performance validity parameter for reaction time is described, using a set of malingering-indices ("Slick-criteria"), and 3 independent samples of participants (total n =893). The Slick-criteria yield an estimate of the probability of malingering based on the presence of an external incentive, evidence from neuropsychological testing, from self-report and clinical data. In study (1) a validity parameter is derived using reaction time data of a sample, composed of inpatients with recent severe brain lesions not involved in litigation and of litigants with and without brain lesion. In study (2) the validity parameter is tested in an independent sample of litigants. In study (3) the parameter is applied to an independent sample comprising cooperative and non-cooperative testees. Logistic regression analysis led to a derived validity parameter based on median reaction time and standard deviation. It performed satisfactorily in studies (2) and (3) (study 2 sensitivity=0.94, specificity=1.00; study 3 sensitivity=0.79, specificity=0.87). The findings suggest that median reaction time and standard deviation may be used as indicators of negative response bias. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Transition Manifolds of Complex Metastable Systems: Theory and Data-Driven Computation of Effective Dynamics.

PubMed

Bittracher, Andreas; Koltai, Péter; Klus, Stefan; Banisch, Ralf; Dellnitz, Michael; Schütte, Christof

2018-01-01

We consider complex dynamical systems showing metastable behavior, but no local separation of fast and slow time scales. The article raises the question of whether such systems exhibit a low-dimensional manifold supporting its effective dynamics. For answering this question, we aim at finding nonlinear coordinates, called reaction coordinates, such that the projection of the dynamics onto these coordinates preserves the dominant time scales of the dynamics. We show that, based on a specific reducibility property, the existence of good low-dimensional reaction coordinates preserving the dominant time scales is guaranteed. Based on this theoretical framework, we develop and test a novel numerical approach for computing good reaction coordinates. The proposed algorithmic approach is fully local and thus not prone to the curse of dimension with respect to the state space of the dynamics. Hence, it is a promising method for data-based model reduction of complex dynamical systems such as molecular dynamics.

Transition Manifolds of Complex Metastable Systems

NASA Astrophysics Data System (ADS)

Bittracher, Andreas; Koltai, Péter; Klus, Stefan; Banisch, Ralf; Dellnitz, Michael; Schütte, Christof

2018-04-01

We consider complex dynamical systems showing metastable behavior, but no local separation of fast and slow time scales. The article raises the question of whether such systems exhibit a low-dimensional manifold supporting its effective dynamics. For answering this question, we aim at finding nonlinear coordinates, called reaction coordinates, such that the projection of the dynamics onto these coordinates preserves the dominant time scales of the dynamics. We show that, based on a specific reducibility property, the existence of good low-dimensional reaction coordinates preserving the dominant time scales is guaranteed. Based on this theoretical framework, we develop and test a novel numerical approach for computing good reaction coordinates. The proposed algorithmic approach is fully local and thus not prone to the curse of dimension with respect to the state space of the dynamics. Hence, it is a promising method for data-based model reduction of complex dynamical systems such as molecular dynamics.

Arm Nerve Conduction Velocity (NCV), Brain NCV, Reaction Time, and Intelligence.

ERIC Educational Resources Information Center

Reed, T. Edward; Jensen, Arthur R.

1991-01-01

Correlations among peripheral nerve conduction velocity (NCV), brain NCV, simple and choice reaction times, and a standard measure of intelligence were investigated for 200 male college students. No correlation was found between any arm NCV and the intelligence score. Neurophysiological bases of human information processing and intelligence are…

QRTEngine: An easy solution for running online reaction time experiments using Qualtrics.

PubMed

Barnhoorn, Jonathan S; Haasnoot, Erwin; Bocanegra, Bruno R; van Steenbergen, Henk

2015-12-01

Performing online behavioral research is gaining increased popularity among researchers in psychological and cognitive science. However, the currently available methods for conducting online reaction time experiments are often complicated and typically require advanced technical skills. In this article, we introduce the Qualtrics Reaction Time Engine (QRTEngine), an open-source JavaScript engine that can be embedded in the online survey development environment Qualtrics. The QRTEngine can be used to easily develop browser-based online reaction time experiments with accurate timing within current browser capabilities, and it requires only minimal programming skills. After introducing the QRTEngine, we briefly discuss how to create and distribute a Stroop task. Next, we describe a study in which we investigated the timing accuracy of the engine under different processor loads using external chronometry. Finally, we show that the QRTEngine can be used to reproduce classic behavioral effects in three reaction time paradigms: a Stroop task, an attentional blink task, and a masked-priming task. These findings demonstrate that QRTEngine can be used as a tool for conducting online behavioral research even when this requires accurate stimulus presentation times.

A Novel Assessment of Braking Reaction Time Following THA Using a New Fully Interactive Driving Simulator.

PubMed

Ruel, Allison V; Lee, Yuo-Yu; Boles, John; Boettner, Friedrich; Su, Edwin; Westrich, Geoffrey H

2015-07-01

After total hip replacement surgery, patients are eager to resume the activities of daily life, particularly driving. Most surgeons recommend waiting 6 weeks after surgery to resume driving; however, there is no evidence to indicate that patients cannot resume driving earlier. Our purpose was to evaluate when in the recovery period following THA that patients regain or improve upon their preoperative braking reaction time, allowing them to safely resume driving. We measured and compared pre- and postoperative braking reaction times of 90 patients from 3 different surgeons using a Fully Interactive Driving Simulator (Simulator Systems International, Tulsa, OK). We defined a return to safe braking reaction time as a return to a time value that is either equal to or less than the preoperative braking reaction time. Patients tested at 2 and 3 weeks after surgery had slower braking reaction times than preoperative times by an average of 0.069 and 0.009 s, respectively. At 4 weeks after surgery, however, patients improved their reaction times by 0.035 s (p = 0.0398). In addition, at 2, 3, and 4 weeks postoperatively, the results also demonstrated that patient less than 70 years of age recovered faster. Based upon the results of this study, most patients should be allowed to return to driving 4 weeks following minimally invasive primary total hip arthroplasty.

Kinetic and mechanism formation reaction of complex compound Cu with di-n-buthildithiocarbamate (dbdtc) ligand

NASA Astrophysics Data System (ADS)

Haryani, S.; Kurniawan, C.; Kasmui

2018-04-01

Synthesis of complex compound is one field of research which intensively studied. Metal-dithiocarbamate complexes find wide-ranging applications in nanomaterial and metal separation science, and have potential use as chemotherapeutic, pesticides, and as additives to lubricants. However, the information about is reaction kinetic and mechanism are very much lacking. The research and analyzes results show that reaction synthesis ligand DBDTC and complex compounds Cu-DBDTC. Optimum reaction condition of formation of complex compounds Cu with DBDTC at pH=3, [DBDTC] = 4.10-3 M, and the time of reaction 5 minutes. Based the analysis varian reaction of complex compounds at pH 3 and 4, diffrence significance at the other pH: 5; 5,5; 6; 6,5 ; 7; and 8. The various of mole with reactants comosition difference sigbificance, those the time reaction for 5 and 6 minutes diffrence by significance with the other time, it is 3,4,8, and 10 minutes. The great product to at condition pH 6, the time optimum at 5 minutes and molar ratio of logam: ligand = 1:2. The reaction kinetic equation of complex compound Cu with chelathing ligand DBDTC is V=0.917106 [Cu2+]0.87921 [DBDTC]2.03021. Based on the kinetic data, and formed complex compounds estimation, the mechanism explaining by 2 stages. In the first stage formation of [Cu(DBDTC)], and then [Cu(DBDTC)2] with the last structure geomethry planar rectangle. The result of this research will be more useful if an effort is being done in reaction mechanism by chemical computation method for obtain intermediate, and for constant “k” in same stage, k1.k2. and compound complex constanta (β).

Urea-based hydrothermal synthesis of LiNi0.5Co0.2Mn0.3O2 cathode material for Li-ion battery

NASA Astrophysics Data System (ADS)

Shi, Yang; Zhang, Minghao; Fang, Chengcheng; Meng, Ying Shirley

2018-08-01

A urea-based hydrothermal approach has been applied to synthesize LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode materials with focus on investigating the influence of the reaction conditions on their electrochemical performance. The compositions of the carbonate precursor are precisely controlled by tuning urea concentration, hydrothermal reaction temperature, and time. The mole ratio between urea and transition metal ions and reaction temperature influence the composition of the precursor; while the reaction time influences the electrochemical performance of the final product. The optimized materials show better cyclability and rate capability compared with the materials synthesized with other hydrothermal reaction conditions. The enhancement is attributed to the larger Li+ diffusion coefficient and lower charge transfer resistance, which are due to the lower degree of Li/Ni cation mixing and more uniform distribution of transition metal ions. This work is a systematic study on the synthesis of NCM523 cathode material by a urea-based hydrothermal approach.

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

Wu, Fuke, E-mail: wufuke@mail.hust.edu.cn; Tian, Tianhai, E-mail: tianhai.tian@sci.monash.edu.au; Rawlings, James B., E-mail: james.rawlings@wisc.edu

The frequently used reduction technique is based on the chemical master equation for stochastic chemical kinetics with two-time scales, which yields the modified stochastic simulation algorithm (SSA). For the chemical reaction processes involving a large number of molecular species and reactions, the collection of slow reactions may still include a large number of molecular species and reactions. Consequently, the SSA is still computationally expensive. Because the chemical Langevin equations (CLEs) can effectively work for a large number of molecular species and reactions, this paper develops a reduction method based on the CLE by the stochastic averaging principle developed in themore » work of Khasminskii and Yin [SIAM J. Appl. Math. 56, 1766–1793 (1996); ibid. 56, 1794–1819 (1996)] to average out the fast-reacting variables. This reduction method leads to a limit averaging system, which is an approximation of the slow reactions. Because in the stochastic chemical kinetics, the CLE is seen as the approximation of the SSA, the limit averaging system can be treated as the approximation of the slow reactions. As an application, we examine the reduction of computation complexity for the gene regulatory networks with two-time scales driven by intrinsic noise. For linear and nonlinear protein production functions, the simulations show that the sample average (expectation) of the limit averaging system is close to that of the slow-reaction process based on the SSA. It demonstrates that the limit averaging system is an efficient approximation of the slow-reaction process in the sense of the weak convergence.« less

Effect of a perturbation-based balance training program on compensatory stepping and grasping reactions in older adults: a randomized controlled trial.

PubMed

Mansfield, Avril; Peters, Amy L; Liu, Barbara A; Maki, Brian E

2010-04-01

Compensatory stepping and grasping reactions are prevalent responses to sudden loss of balance and play a critical role in preventing falls. The ability to execute these reactions effectively is impaired in older adults. The purpose of this study was to evaluate a perturbation-based balance training program designed to target specific age-related impairments in compensatory stepping and grasping balance recovery reactions. This was a double-blind randomized controlled trial. The study was conducted at research laboratories in a large urban hospital. Thirty community-dwelling older adults (aged 64-80 years) with a recent history of falls or self-reported instability participated in the study. Participants were randomly assigned to receive either a 6-week perturbation-based (motion platform) balance training program or a 6-week control program involving flexibility and relaxation training. Features of balance reactions targeted by the perturbation-based program were: (1) multi-step reactions, (2) extra lateral steps following anteroposterior perturbations, (3) foot collisions following lateral perturbations, and (4) time to complete grasping reactions. The reactions were evoked during testing by highly unpredictable surface translation and cable pull perturbations, both of which differed from the perturbations used during training. /b> Compared with the control program, the perturbation-based training led to greater reductions in frequency of multi-step reactions and foot collisions that were statistically significant for surface translations but not cable pulls. The perturbation group also showed significantly greater reduction in handrail contact time compared with the control group for cable pulls and a possible trend in this direction for surface translations. Further work is needed to determine whether a maintenance program is needed to retain the training benefits and to assess whether these benefits reduce fall risk in daily life. Perturbation-based training shows promise as an effective intervention to improve the ability of older adults to prevent themselves from falling when they lose their balance.

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

Li, Xinle

In conclusion, we have for the first time developed a novel solid base catalyst, Ndoped MOF-253 derived porous carbons (Cz-MOF-253). Cz-MOF-253 is highly porous and exhibit high efficiency in Knoevenagel condensation reaction. Furthermore, Cz-MOF-253 is robust and can be reused up to five times. In comparison, the analogous nitrogen-free catalyst-Cz-DUT-5, and other nitrogen- MOFs derived carbon showed an inferior performance. Moreover, the high basicity and porous nature enable the design of bifunctional catalyst and facilitate tandem condensation-hydrogenation reactions. This work delineates the first attempt that demonstrates MOF-derived carbons as solid base catalyst and its potential application in tandem catalysis. Futuremore » work on exploring new catalytic reactions based on such porous Lewis basic MOF-derived carbons is currently underway.« less

Approaching near real-time biosensing: microfluidic microsphere based biosensor for real-time analyte detection.

PubMed

Cohen, Noa; Sabhachandani, Pooja; Golberg, Alexander; Konry, Tania

2015-04-15

In this study we describe a simple lab-on-a-chip (LOC) biosensor approach utilizing well mixed microfluidic device and a microsphere-based assay capable of performing near real-time diagnostics of clinically relevant analytes such cytokines and antibodies. We were able to overcome the adsorption kinetics reaction rate-limiting mechanism, which is diffusion-controlled in standard immunoassays, by introducing the microsphere-based assay into well-mixed yet simple microfluidic device with turbulent flow profiles in the reaction regions. The integrated microsphere-based LOC device performs dynamic detection of the analyte in minimal amount of biological specimen by continuously sampling micro-liter volumes of sample per minute to detect dynamic changes in target analyte concentration. Furthermore we developed a mathematical model for the well-mixed reaction to describe the near real time detection mechanism observed in the developed LOC method. To demonstrate the specificity and sensitivity of the developed real time monitoring LOC approach, we applied the device for clinically relevant analytes: Tumor Necrosis Factor (TNF)-α cytokine and its clinically used inhibitor, anti-TNF-α antibody. Based on the reported results herein, the developed LOC device provides continuous sensitive and specific near real-time monitoring method for analytes such as cytokines and antibodies, reduces reagent volumes by nearly three orders of magnitude as well as eliminates the washing steps required by standard immunoassays. Copyright © 2014 Elsevier B.V. All rights reserved.

Development of interactive graphic user interfaces for modeling reaction-based biogeochemical processes in batch systems with BIOGEOCHEM

NASA Astrophysics Data System (ADS)

Chang, C.; Li, M.; Yeh, G.

2010-12-01

The BIOGEOCHEM numerical model (Yeh and Fang, 2002; Fang et al., 2003) was developed with FORTRAN for simulating reaction-based geochemical and biochemical processes with mixed equilibrium and kinetic reactions in batch systems. A complete suite of reactions including aqueous complexation, adsorption/desorption, ion-exchange, redox, precipitation/dissolution, acid-base reactions, and microbial mediated reactions were embodied in this unique modeling tool. Any reaction can be treated as fast/equilibrium or slow/kinetic reaction. An equilibrium reaction is modeled with an implicit finite rate governed by a mass action equilibrium equation or by a user-specified algebraic equation. A kinetic reaction is modeled with an explicit finite rate with an elementary rate, microbial mediated enzymatic kinetics, or a user-specified rate equation. None of the existing models has encompassed this wide array of scopes. To ease the input/output learning curve using the unique feature of BIOGEOCHEM, an interactive graphic user interface was developed with the Microsoft Visual Studio and .Net tools. Several user-friendly features, such as pop-up help windows, typo warning messages, and on-screen input hints, were implemented, which are robust. All input data can be real-time viewed and automated to conform with the input file format of BIOGEOCHEM. A post-processor for graphic visualizations of simulated results was also embedded for immediate demonstrations. By following data input windows step by step, errorless BIOGEOCHEM input files can be created even if users have little prior experiences in FORTRAN. With this user-friendly interface, the time effort to conduct simulations with BIOGEOCHEM can be greatly reduced.

Systemic effect of mineral aggregate-based cements: histopathological analysis in rats

PubMed Central

Garcia, Lucas da Fonseca Roberti; Huck, Claudia; Magalhães, Fernando Augusto Cintra; de Souza, Pedro Paulo Chaves; de Souza Costa, Carlos Alberto

2017-01-01

Abstract Objective: Several studies reported the local tissue reaction caused by mineral aggregate-based cements. However, few studies have investigated the systemic effects promoted by these cements on liver and kidney when directly applied to connective tissue. The purpose of this in vivo study was to investigate the systemic effect of mineral aggregate-based cements on the livers and kidneys of rats. Material and Methods: Samples of Mineral Trioxide Aggregate (MTA) and a calcium aluminate-based cement (EndoBinder) containing different radiopacifiers were implanted into the dorsum of 40 rats. After 7 and 30 d, samples of subcutaneous, liver and kidney tissues were submitted to histopathological analysis. A score (0-3) was used to grade the inflammatory reaction. Blood samples were collected to evaluate changes in hepatic and renal functions of animals. Results: The moderate inflammatory reaction (2) observed for 7 d in the subcutaneous tissue decreased with time for all cements. The thickness of inflammatory capsules also presented a significant decrease with time (P<.05). Systemically, all cements caused adverse inflammatory reactions in the liver and kidney, being more evident for MTA, persisting until the end of the analysis. Liver functions increased significantly for MTA during 30 d (P<.05). Conclusion: The different cements induced to a locally limited inflammatory reaction. However, from the systemic point of view, the cements promoted significant inflammatory reactions in the liver and kidney. For MTA, the reactions were more accentuated. PMID:29211283

Oxidation of benzoin catalyzed by oxovanadium(IV) schiff base complexes

PubMed Central

2013-01-01

Background The oxidative transformation of benzoin to benzil has been accomplished by the use of a wide variety of reagents or catalysts and different reaction procedures. The conventional oxidizing agents yielded mainly benzaldehyde or/and benzoic acid and only a trace amount of benzil. The limits of practical utilization of these reagents involves the use of stoichiometric amounts of corrosive acids or toxic metallic reagents, which in turn produce undesirable waste materials and required high reaction temperatures. In recent years, vanadium complexes have attracted much attention for their potential utility as catalysts for various types of reactions. Results Active and selective catalytic systems of new unsymmetrical oxovanadium(IV) Schiff base complexes for the oxidation of benzoin is reported. The Schiff base ligands are derived between 2-aminoethanol and 2-hydroxy-1-naphthaldehyde (H2L1) or 3-ethoxy salicylaldehyde (H2L3); and 2-aminophenol and 3-ethoxysalicylaldehyde (H2L2) or 2-hydroxy-1-naphthaldehyde (H2L4). The unsymmetrical Schiff bases behave as tridentate dibasic ONO donor ligands. Reaction of these Schiff base ligands with oxovanadyl sulphate afforded the mononuclear oxovanadium(IV) complexes (VIVOLx.H2O), which are characterized by various physico-chemical techniques. The catalytic oxidation activities of these complexes for benzoin were evaluated using H2O2 as an oxidant. The best reaction conditions are obtained by considering the effect of solvent, reaction time and temperature. Under the optimized reaction conditions, VOL4 catalyst showed high conversion (>99%) with excellent selectivity to benzil (~100%) in a shorter reaction time compared to the other catalysts considered. Conclusion Four tridentate ONO type Schiff base ligands were synthesized. Complexation of these ligands with vanadyl(IV) sulphate leads to the formation of new oxovanadium(IV) complexes of type VIVOL.H2O. Elemental analyses and spectral data of the free ligands and their oxovanadium(IV) complexes were found to be in good agreement with their structures, indicating high purity of all the compounds. Oxovanadium complexes were screened for the oxidation of benzoin to benzil using H2O2 as oxidant. The effect of time, solvent and temperature were optimized to obtain maximum yield. The catalytic activity results demonstrate that these catalytic systems are both highly active and selective for the oxidation of benzoin under mild reaction conditions. PMID:23294561

Oxidation of benzoin catalyzed by oxovanadium(IV) schiff base complexes.

PubMed

Alsalim, Tahseen A; Hadi, Jabbar S; Ali, Omar N; Abbo, Hanna S; Titinchi, Salam Jj

2013-01-07

The oxidative transformation of benzoin to benzil has been accomplished by the use of a wide variety of reagents or catalysts and different reaction procedures. The conventional oxidizing agents yielded mainly benzaldehyde or/and benzoic acid and only a trace amount of benzil. The limits of practical utilization of these reagents involves the use of stoichiometric amounts of corrosive acids or toxic metallic reagents, which in turn produce undesirable waste materials and required high reaction temperatures.In recent years, vanadium complexes have attracted much attention for their potential utility as catalysts for various types of reactions. Active and selective catalytic systems of new unsymmetrical oxovanadium(IV) Schiff base complexes for the oxidation of benzoin is reported. The Schiff base ligands are derived between 2-aminoethanol and 2-hydroxy-1-naphthaldehyde (H2L1) or 3-ethoxy salicylaldehyde (H2L3); and 2-aminophenol and 3-ethoxysalicylaldehyde (H2L2) or 2-hydroxy-1-naphthaldehyde (H2L4). The unsymmetrical Schiff bases behave as tridentate dibasic ONO donor ligands. Reaction of these Schiff base ligands with oxovanadyl sulphate afforded the mononuclear oxovanadium(IV) complexes (VIVOLx.H2O), which are characterized by various physico-chemical techniques.The catalytic oxidation activities of these complexes for benzoin were evaluated using H2O2 as an oxidant. The best reaction conditions are obtained by considering the effect of solvent, reaction time and temperature. Under the optimized reaction conditions, VOL4 catalyst showed high conversion (>99%) with excellent selectivity to benzil (~100%) in a shorter reaction time compared to the other catalysts considered. Four tridentate ONO type Schiff base ligands were synthesized. Complexation of these ligands with vanadyl(IV) sulphate leads to the formation of new oxovanadium(IV) complexes of type VIVOL.H2O.Elemental analyses and spectral data of the free ligands and their oxovanadium(IV) complexes were found to be in good agreement with their structures, indicating high purity of all the compounds.Oxovanadium complexes were screened for the oxidation of benzoin to benzil using H2O2 as oxidant. The effect of time, solvent and temperature were optimized to obtain maximum yield. The catalytic activity results demonstrate that these catalytic systems are both highly active and selective for the oxidation of benzoin under mild reaction conditions.

An efficient copper-based magnetic nanocatalyst for the fixation of carbon dioxide at atmospheric pressure.

PubMed

Sharma, Rakesh Kumar; Gaur, Rashmi; Yadav, Manavi; Goswami, Anandarup; Zbořil, Radek; Gawande, Manoj B

2018-01-30

In the last few decades, the emission of carbon dioxide (CO 2 ) in the environment has caused havoc across the globe. One of the most promising strategies for fixation of CO 2 is the cycloaddition reaction between epoxides and CO 2 to produce cyclic carbonates. For the first time, we have fabricated copper-based magnetic nanocatalyst and have applied for the CO 2 fixation. The prepared catalyst was thoroughly characterized using various techniques including XRD, FT-IR, TEM, FE-SEM, XPS, VSM, ICP-OES and elemental mapping. The reactions proceeded at atmospheric pressure, relatively lower temperature, short reaction time, solvent- less and organic halide free reaction conditions. Additionally, the ease of recovery through an external magnet, reusability of the catalyst and excellent yields of the obtained cyclic carbonates make the present protocol practical and sustainable.

Real-time monitoring of enzyme-free strand displacement cascades by colorimetric assays.

PubMed

Duan, Ruixue; Wang, Boya; Hong, Fan; Zhang, Tianchi; Jia, Yongmei; Huang, Jiayu; Hakeem, Abdul; Liu, Nannan; Lou, Xiaoding; Xia, Fan

2015-03-19

The enzyme-free toehold-mediated strand displacement reaction has shown potential for building programmable DNA circuits, biosensors, molecular machines and chemical reaction networks. Here we report a simple colorimetric method using gold nanoparticles as signal generators for the real-time detection of the product of the strand displacement cascade. During the process the assembled gold nanoparticles can be separated, resulting in a color change of the solution. This assay can also be applied in complex mixtures, fetal bovine serum, and to detect single-base mismatches. These results suggest that this method could be of general utility to monitor more complex enzyme-free strand displacement reaction-based programmable systems or for further low-cost diagnostic applications.

Thermal decomposition of condensed-phase nitromethane from molecular dynamics from ReaxFF reactive dynamics.

PubMed

Han, Si-ping; van Duin, Adri C T; Goddard, William A; Strachan, Alejandro

2011-05-26

We studied the thermal decomposition and subsequent reaction of the energetic material nitromethane (CH(3)NO(2)) using molecular dynamics with ReaxFF, a first principles-based reactive force field. We characterize the chemistry of liquid and solid nitromethane at high temperatures (2000-3000 K) and density 1.97 g/cm(3) for times up to 200 ps. At T = 3000 K the first reaction in the decomposition of nitromethane is an intermolecular proton transfer leading to CH(3)NOOH and CH(2)NO(2). For lower temperatures (T = 2500 and 2000 K) the first reaction during decomposition is often an isomerization reaction involving the scission of the C-N bond the formation of a C-O bond to form methyl nitrate (CH(3)ONO). Also at very early times we observe intramolecular proton transfer events. The main product of these reactions is H(2)O which starts forming following those initiation steps. The appearance of H(2)O marks the beginning of the exothermic chemistry. Recent quantum-mechanics-based molecular dynamics simulations on the chemical reactions and time scales for decomposition of a crystalline sample heated to T = 3000 K for a few picoseconds are in excellent agreement with our results, providing an important, direct validation of ReaxFF.

Detonation Reaction Zones in Condensed Explosives

NASA Astrophysics Data System (ADS)

Tarver, Craig M.

2006-07-01

Experimental measurements using nanosecond time resolved embedded gauges and laser interferometric techniques, combined with Non-Equilibrium Zeldovich - von Neumann - Doling (NEZND) theory and Ignition and Growth reactive flow hydrodynamic modeling, have revealed the average pressure/particle velocity states attained in reaction zones of self-sustaining detonation waves in several solid and liquid explosives. The time durations of these reaction zone processes are discussed for explosives based on pentaerythritol tetranitrate (PETN), nitromethane, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), triaminitrinitrobenzene(TATB) and trinitrotoluene (TNT).

Comparative efficacy of microwave, visible light and ultrasound irradiation for green synthesis of dihydropyrimidinones in fruit juice medium

NASA Astrophysics Data System (ADS)

Pramanik, Tanay; Padan, Simarjit Kaur; Gupta, Richa; Bedi, Pooja; Singh, Gurinderpal

2017-07-01

Dihydropyrimidinones (DHPM) were synthesized via multi component condensation reaction employing urea, ethyl acetoacetate and aromatic aldehydes as reactants. Apple, pomegranate, grape juice were used individually as biodegradable, eco friendly, and green reaction medium whereas microwave, visible light and ultrasound irradiation were applied individually as green source of energy for carrying out the aforesaid reactions. It was observed that the reactions under microwave irradiation were taking minimum time to go for completion whereas the reactions under ultrasound and visible light irradiation were taking approximately same time duration to form products. This is the first of its kind study where the three different reaction methodologies based on three different sources of green energies were compared with each other for their effectiveness and efficiency towards multi component condensation reactions.

Simple real-time computerized tasks for detection of malingering among murderers with schizophrenia.

PubMed

Kertzman, Semion; Grinspan, Haim; Birger, Moshe; Shliapnikov, Nina; Alish, Yakov; Ben Nahum, Zeev; Mester, Roberto; Kotler, Moshe

2006-01-01

It is our contention that computer-based two-alternative forced choice techniques can be useful tools for the detection of patients with schizophrenia who feign acute psychotic symptoms and cognitive impairment as opposed to patients with schizophrenia with a true active psychosis. In our experiment, Visual Simple and Choice Reaction Time tasks were used. Reaction time in milliseconds was recorded and accuracy rate was obtained for all subjects' responses. Both types of task were administered to 27 patients with schizophrenia suspected of having committed murder. Patients with schizophrenia who were clinically assessed as malingerers achieved significantly fewer correct results, were significantly slower and less consistent in their reaction time. Congruence of performance between the Simple and Choice tasks was an additional parameter for the accurate diagnosis of malingering. The four parameters of both tests (accuracy of response, reaction time, standard deviation of reaction time and task congruency) are simple and constitute a user-friendly means for the detection of malingering in forensic practice. Another advantage of this procedure is that the software automatically measures and evaluates all the parameters.

Integrating Pilates Exercise into an Exercise Program for 65+ Year-Old Women to Reduce Falls

PubMed Central

Irez, Gonul Babayigit; Ozdemir, Recep Ali; Evin, Ruya; Irez, Salih Gokhan; Korkusuz, Feza

2011-01-01

The purpose of this study was to determine if Pilates exercise could improve dynamic balance, flexibility, reaction time and muscle strength in order to reduce the number of falls among older women. 60 female volunteers over the age of 65 from a residential home in Ankara participated in this study. Participants joined a 12-week series of 1-hour Pilates sessions three times per week. Dynamic balance, flexibility, reaction time and muscle strength were measured before and after the program. The number of falls before and during the 12-week period was also recorded. Dynamic balance, flexibility, reaction time and muscle strength improved (p < 0. 05) in the exercise group when compared to the non-exercise group. In conclusion, Pilates exercises are effective in improving dynamic balance, flexibility, reaction time, and muscle strength as well as decreasing the propensity to fall in older women. Key points Pilates-based exercises improve dynamic balance, reaction time and muscle strength in the elderly. Pilates exercise may reduce the number of falls in elderly women by increasing these fitness parameters. PMID:24149302

Dynamical Aspects of Quasifission Process in Heavy-Ion Reactions

NASA Astrophysics Data System (ADS)

Knyazheva, G. N.; Itkis, I. M.; Kozulin, E. M.

2015-06-01

The study of mass-energy distributions of binary fragments obtained in the reactions of 36S, 48Ca, 58Fe and 64Ni ions with the 232Th, 238U, 244Pu and 248Cm at energies below and above the Coulomb barrier is presented. For all the reactions the main component of the distributions corresponds to asymmetrical mass division typical for asymmetric quasifission process. To describe the quasifission mass distribution the simple method has been proposed. This method is based on the driving potential of the system and time dependent mass drift. This procedure allows to estimate QF time scale from the measured mass distributions. It has been found that the QF time exponentially decreases when the reaction Coulomb factor Z1Z2 increases.

On the Locus of Speed-Accuracy Trade-Off in Reaction Time: Inferences From the Lateralized Readiness Potential

ERIC Educational Resources Information Center

Rinkenauer, Gerhard; Osman, Allen; Ulrich, Rolf; Muller-Gethmann, Hiltraut; Mattes, Stefan

2004-01-01

Lateralized readiness potentials (LRPs) were used to determine the stage(s) of reaction time (RT) responsible for speed-accuracy trade-offs (SATs). Speeded decisions based on several types of information were examined in 3 experiments, involving, respectively, a line discrimination task, lexical decisions, and an Erikson flanker task. Three levels…

A global approach for using kinematic redundancy to minimize base reactions of manipulators

NASA Technical Reports Server (NTRS)

Chung, C. L.; Desa, S.

1989-01-01

An important consideration in the use of manipulators in microgravity environments is the minimization of the base reactions, i.e. the magnitude of the force and the moment exerted by the manipulator on its base as it performs its tasks. One approach which was proposed and implemented is to use the redundant degree of freedom in a kinematically redundant manipulator to plan manipulator trajectories to minimize base reactions. A global approach was developed for minimizing the magnitude of the base reactions for kinematically redundant manipulators which integrates the Partitioned Jacobian method of redundancy resolution, a 4-3-4 joint-trajectory representation and the minimization of a cost function which is the time-integral of the magnitude of the base reactions. The global approach was also compared with a local approach developed earlier for the case of point-to-point motion of a three degree-of-freedom planar manipulator with one redundant degree-of-freedom. The results show that the global approach is more effective in reducing and smoothing the base force while the local approach is superior in reducing the base moment.

Transport—Reaction process in the reaction of flue gas desulfurization

NASA Astrophysics Data System (ADS)

Yan, Yan; Peng, Xiaofeng; Lee, Duu Jong

2000-12-01

A theoretical investigation was conducted to study the transport-reaction process in the spray-drying flue gas desulfurization. A transport-reaction model of single particle was proposed, which considered the water evaporation from the surface of droplet and the reaction at the same time. Based on this model, the reaction rate and the absorbent utilization can be calculated. The most appropriate particle radius and the initial absorbent concentration can be deduced through comparing the wet lifetime with the residence time, the result shows in the case that the partial pressure of vapor in the bulk flue gas is 2000Pa, the optimum initial radius and absorbent concentration are 210 310 µ m and 23% respectively. The model can supply the optimum parameters for semi-dry FGD system designed.

Reaction time effects in lab- versus Web-based research: Experimental evidence.

PubMed

Hilbig, Benjamin E

2016-12-01

Although Web-based research is now commonplace, it continues to spur skepticism from reviewers and editors, especially whenever reaction times are of primary interest. Such persistent preconceptions are based on arguments referring to increased variation, the limits of certain software and technologies, and a noteworthy lack of comparisons (between Web and lab) in fully randomized experiments. To provide a critical test, participants were randomly assigned to complete a lexical decision task either (a) in the lab using standard experimental software (E-Prime), (b) in the lab using a browser-based version (written in HTML and JavaScript), or (c) via the Web using the same browser-based version. The classical word frequency effect was typical in size and corresponded to a very large effect in all three conditions. There was no indication that the Web- or browser-based data collection was in any way inferior. In fact, if anything, a larger effect was obtained in the browser-based conditions than in the condition relying on standard experimental software. No differences between Web and lab (within the browser-based conditions) could be observed, thus disconfirming any substantial influence of increased technical or situational variation. In summary, the present experiment contradicts the still common preconception that reaction time effects of only a few hundred milliseconds cannot be detected in Web experiments.

Organocatalytic aza-Michael/retro-aza-Michael reaction: pronounced chirality amplification in aza-Michael reaction and racemization via retro-aza-Michael reaction.

PubMed

Cai, Yong-Feng; Li, Li; Luo, Meng-Xian; Yang, Ke-Fang; Lai, Guo-Qiao; Jiang, Jian-Xiong; Xu, Li-Wen

2011-05-01

A detailed experimental investigation of an aza-Michael reaction of aniline and chalcone is presented. A series of Cinchona alkaloid-derived organocatalysts with different functional groups were prepared and used in the aza-Michael and retro-aza-Michael reaction. There was an interesting finding that a complete reversal of stereoselectivity when a benzoyl group was introduced to the cinchonine and cinchonidine. The chirality amplification vs. time proceeds in the quinine-derived organocatalyst containing silicon-based bulky group, QN-TBS, -catalyzed aza-Michael reaction under solvent-free conditions. In addition, we have demonstrated for the first time that racemization was occurred in suitable solvents under mild conditions due to retro-aza-Michael reaction of the Michael adduct of aniline with chalcone. These indicate the equilibrium of retro-aza-Michael reaction and aza-Michael reaction produce the happening of chirality amplification in aza-Michael reaction and racemization via retro-aza-Michael reaction under different conditions, which would be beneficial to the development of novel chiral catalysts for the aza-Michael reactions. Copyright © 2011 Wiley-Liss, Inc.

Development and validation of a SYBR Green I-based real-time polymerase chain reaction method for detection of haptoglobin gene deletion in clinical materials.

PubMed

Soejima, Mikiko; Tsuchiya, Yuji; Egashira, Kouichi; Kawano, Hiroyuki; Sagawa, Kimitaka; Koda, Yoshiro

2010-06-01

Anhaptoglobinemic patients run the risk of severe anaphylactic transfusion reaction because they produce serum haptoglobin (Hp) antibodies. Being homozygous for the Hp gene deletion (HP(del)) is the only known cause of congenital anhaptoglobinemia, and clinical diagnosis of HP(del) before transfusion is important to prevent anaphylactic shock. We recently developed a 5'-nuclease (TaqMan) real-time polymerase chain reaction (PCR) method. A SYBR Green I-based duplex real-time PCR assay using two forward primers and a common reverse primer followed by melting curve analysis was developed to determine HP(del) zygosity in a single tube. In addition, to obviate initial DNA extraction, we examined serially diluted blood samples as PCR templates. Allelic discrimination of HP(del) yielded optimal results at blood sample dilutions of 1:64 to 1:1024. The results from 2231 blood samples were fully concordant with those obtained by the TaqMan-based real-time PCR method. The detection rate of the HP(del) allele by the SYBR Green I-based method is comparable with that using the TaqMan-based method. This method is readily applicable due to its low initial cost and analyzability using economical real-time PCR machines and is suitable for high-throughput analysis as an alternative method for allelic discrimination of HP(del).

SQERTSS: Dynamic rank based throttling of transition probabilities in kinetic Monte Carlo simulations

DOE PAGES

Danielson, Thomas; Sutton, Jonathan E.; Hin, Céline; ...

2017-06-09

Lattice based Kinetic Monte Carlo (KMC) simulations offer a powerful simulation technique for investigating large reaction networks while retaining spatial configuration information, unlike ordinary differential equations. However, large chemical reaction networks can contain reaction processes with rates spanning multiple orders of magnitude. This can lead to the problem of “KMC stiffness” (similar to stiffness in differential equations), where the computational expense has the potential to be overwhelmed by very short time-steps during KMC simulations, with the simulation spending an inordinate amount of KMC steps / cpu-time simulating fast frivolous processes (FFPs) without progressing the system (reaction network). In order tomore » achieve simulation times that are experimentally relevant or desired for predictions, a dynamic throttling algorithm involving separation of the processes into speed-ranks based on event frequencies has been designed and implemented with the intent of decreasing the probability of FFP events, and increasing the probability of slow process events -- allowing rate limiting events to become more likely to be observed in KMC simulations. This Staggered Quasi-Equilibrium Rank-based Throttling for Steady-state (SQERTSS) algorithm designed for use in achieving and simulating steady-state conditions in KMC simulations. Lastly, as shown in this work, the SQERTSS algorithm also works for transient conditions: the correct configuration space and final state will still be achieved if the required assumptions are not violated, with the caveat that the sizes of the time-steps may be distorted during the transient period.« less

SQERTSS: Dynamic rank based throttling of transition probabilities in kinetic Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Danielson, Thomas; Sutton, Jonathan E.; Hin, Céline; Savara, Aditya

2017-10-01

Lattice based Kinetic Monte Carlo (KMC) simulations offer a powerful simulation technique for investigating large reaction networks while retaining spatial configuration information, unlike ordinary differential equations. However, large chemical reaction networks can contain reaction processes with rates spanning multiple orders of magnitude. This can lead to the problem of "KMC stiffness" (similar to stiffness in differential equations), where the computational expense has the potential to be overwhelmed by very short time-steps during KMC simulations, with the simulation spending an inordinate amount of KMC steps/CPU time simulating fast frivolous processes (FFPs) without progressing the system (reaction network). In order to achieve simulation times that are experimentally relevant or desired for predictions, a dynamic throttling algorithm involving separation of the processes into speed-ranks based on event frequencies has been designed and implemented with the intent of decreasing the probability of FFP events, and increasing the probability of slow process events-allowing rate limiting events to become more likely to be observed in KMC simulations. This Staggered Quasi-Equilibrium Rank-based Throttling for Steady-state (SQERTSS) algorithm is designed for use in achieving and simulating steady-state conditions in KMC simulations. As shown in this work, the SQERTSS algorithm also works for transient conditions: the correct configuration space and final state will still be achieved if the required assumptions are not violated, with the caveat that the sizes of the time-steps may be distorted during the transient period.

Fluid dynamic modeling of nano-thermite reactions

NASA Astrophysics Data System (ADS)

Martirosyan, Karen S.; Zyskin, Maxim; Jenkins, Charles M.; Yuki Horie, Yasuyuki

2014-03-01

This paper presents a direct numerical method based on gas dynamic equations to predict pressure evolution during the discharge of nanoenergetic materials. The direct numerical method provides for modeling reflections of the shock waves from the reactor walls that generates pressure-time fluctuations. The results of gas pressure prediction are consistent with the experimental evidence and estimates based on the self-similar solution. Artificial viscosity provides sufficient smoothing of shock wave discontinuity for the numerical procedure. The direct numerical method is more computationally demanding and flexible than self-similar solution, in particular it allows study of a shock wave in its early stage of reaction and allows the investigation of "slower" reactions, which may produce weaker shock waves. Moreover, numerical results indicate that peak pressure is not very sensitive to initial density and reaction time, providing that all the material reacts well before the shock wave arrives at the end of the reactor.

Fluid dynamic modeling of nano-thermite reactions

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

Martirosyan, Karen S., E-mail: karen.martirosyan@utb.edu; Zyskin, Maxim; Jenkins, Charles M.

2014-03-14

This paper presents a direct numerical method based on gas dynamic equations to predict pressure evolution during the discharge of nanoenergetic materials. The direct numerical method provides for modeling reflections of the shock waves from the reactor walls that generates pressure-time fluctuations. The results of gas pressure prediction are consistent with the experimental evidence and estimates based on the self-similar solution. Artificial viscosity provides sufficient smoothing of shock wave discontinuity for the numerical procedure. The direct numerical method is more computationally demanding and flexible than self-similar solution, in particular it allows study of a shock wave in its early stagemore » of reaction and allows the investigation of “slower” reactions, which may produce weaker shock waves. Moreover, numerical results indicate that peak pressure is not very sensitive to initial density and reaction time, providing that all the material reacts well before the shock wave arrives at the end of the reactor.« less

Driving Ability of HMX based Aluminized Explosive Affected by the Reaction Degree of Aluminum Powder

NASA Astrophysics Data System (ADS)

Duan, Yingliang

2017-06-01

Due to the time scale of aluminum reaction, the detonation process of the aluminized explosive becomes very complex, and there is less agreement on the reaction mechanism of aluminum powder. If the reaction of aluminum occurs in the reaction zone, the energy released will further strengthen the work ability of detonation wave. So it is very important for characterizing the detonation parameters and detonation driving ability to accurately understand the role of aluminum powder in the reaction zone. In this paper, detonation driving process of HMX based aluminized explosive was studied by cylinder test, obtaining the expansion track of cylinder wall. In order to further research the reaction degree (λ) of aluminum in the reaction zone, the thermodynamic program VHL was used to calculate the detonation process at different reaction degrees, obtaining the parameters of detonation products thermodynamic state. Using the dynamic software LS-DYNA and the JWL equation of state by fitting the pressure and relative volume relationship, the cylinder test was simulated. Compared with the experimental results, when the reaction degree is 20%, the driving ability is found to be in agreement with measured ones. It is concluded that the driving ability of HMX based aluminized explosive can be more accurately characterized by considering the reaction degree of aluminum powder in the reaction zone.

Cost-effectiveness of one-time genetic testing to minimize lifetime adverse drug reactions.

PubMed

Alagoz, O; Durham, D; Kasirajan, K

2016-04-01

We evaluated the cost-effectiveness of one-time pharmacogenomic testing for preventing adverse drug reactions (ADRs) over a patient's lifetime. We developed a Markov-based Monte Carlo microsimulation model to represent the ADR events in the lifetime of each patient. The base-case considered a 40-year-old patient. We measured health outcomes in life years (LYs) and quality-adjusted LYs (QALYs) and estimated costs using 2013 US$. In the base-case, one-time genetic testing had an incremental cost-effectiveness ratio (ICER) of $43,165 (95% confidence interval (CI) is ($42,769,$43,561)) per additional LY and $53,680 per additional QALY (95% CI is ($53,182,$54,179)), hence under the base-case one-time genetic testing is cost-effective. The ICER values were most sensitive to the average probability of death due to ADR, reduction in ADR rate due to genetic testing, mean ADR rate and cost of genetic testing.

The use of locally optimal trajectory management for base reaction control of robots in a microgravity environment

NASA Technical Reports Server (NTRS)

Lin, N. J.; Quinn, R. D.

1991-01-01

A locally-optimal trajectory management (LOTM) approach is analyzed, and it is found that care should be taken in choosing the Ritz expansion and cost function. A modified cost function for the LOTM approach is proposed which includes the kinetic energy along with the base reactions in a weighted and scale sum. The effects of the modified functions are demonstrated with numerical examples for robots operating in two- and three-dimensional space. It is pointed out that this modified LOTM approach shows good performance, the reactions do not fluctuate greatly, joint velocities reach their objectives at the end of the manifestation, and the CPU time is slightly more than twice the manipulation time.

Persistence of the Intuitive Conception That Heavier Objects Sink More: A Reaction Time Study with Different Levels of Interference

ERIC Educational Resources Information Center

Potvin, Patrice; Masson, Steve; Lafortune, Stéphanie; Cyr, Guillaume

2015-01-01

Recent research efforts have argued for the "persistence" of some of students' frequent scientific misconceptions, even after correct answers are produced. Some of these studies, based on the analysis of reaction times, have recorded latencies for counter-intuitive or incongruent stimuli compared to intuitive or congruent ones. The…

Off-line real-time FTIR analysis of a process step in imipenem production

NASA Astrophysics Data System (ADS)

Boaz, Jhansi R.; Thomas, Scott M.; Meyerhoffer, Steven M.; Staskiewicz, Steven J.; Lynch, Joseph E.; Egan, Richard S.; Ellison, Dean K.

1992-08-01

We have developed an FT-IR method, using a Spectra-Tech Monit-IR 400 systems, to monitor off-line the completion of a reaction in real-time. The reaction is moisture-sensitive and analysis by more conventional methods (normal-phase HPLC) is difficult to reproduce. The FT-IR method is based on the shift of a diazo band when a conjugated beta-diketone is transformed into a silyl enol ether during the reaction. The reaction mixture is examined directly by IR and does not require sample workup. Data acquisition time is less than one minute. The method has been validated for specificity, precision and accuracy. The results obtained by the FT-IR method for known mixtures and in-process samples compare favorably with those from a normal-phase HPLC method.

The Barium Hydroxide-Ammonium Thiocyanate Reaction: A Titrimetric Continuous Variations Experiment.

ERIC Educational Resources Information Center

Harris, Arlo D.

1979-01-01

Presents an experiment for inorganic, organic, or physical chemistry students utilizing acid-base titrimetry to study the stoichiometric of a solid state reaction. Time involved ranges from one to three, three-hour lab periods. (Author/SA)

Definition of simulated driving tests for the evaluation of drivers' reactions and responses.

PubMed

Bartolozzi, Riccardo; Frendo, Francesco

2014-01-01

This article aims at identifying the most significant measures in 2 perception-response (PR) tests performed at a driving simulator: a braking test and a lateral skid test, which were developed in this work. Forty-eight subjects (26 females and 22 males) with a mean age of 24.9 ± 3.0 years were enrolled for this study. They were asked to perform a drive on the driving simulator at the University of Pisa (Italy) following a specific test protocol, including 8-10 braking tests and 8-10 lateral skid tests. Driver input signals and vehicle model signals were recorded during the drives and analyzed to extract measures such as the reaction time, first response time, etc. Following a statistical procedure (based on analysis of variance [ANOVA] and post hoc tests), all test measures (3 for the braking test and 8 for the lateral skid test) were analyzed in terms of statistically significant differences among different drivers. The presented procedure allows evaluation of the capability of a given test to distinguish among different drivers. In the braking test, the reaction time showed a high dispersion among single drivers, leading to just 4.8 percent of statistically significant driver pairs (using the Games-Howell post hoc test), whereas the pedal transition time scored 31.9 percent. In the lateral skid test, 28.5 percent of the 2 × 2 comparisons showed significantly different reaction times, 19.5 percent had different response times, 35.2 percent had a different second peak of the steering wheel signal, and 33 percent showed different values of the integral of the steering wheel signal. For the braking test, which has been widely employed in similar forms in the literature, it was shown how the reaction time, with respect to the pedal transition time, can have a higher dispersion due to the influence of external factors. For the lateral skid test, the following measures were identified as the most significant for application studies: the reaction time for the reaction phase, the second peak of the steering wheel angle for the first instinctive response, and the integral of the steering wheel angle for the complete response. The methodology used to analyze the test measures was founded on statistically based and objective evaluation criteria and could be applied to other tests. Even if obtained with a fixed-base simulator, the obtained results represent useful information for applications of the presented PR tests in experimental campaigns with driving simulators.

Reactions in Droplets in Microfluidic Channels

PubMed Central

Song, Helen; Chen, Delai L.; Ismagilov, Rustem F.

2006-01-01

Fundamental and applied research in chemistry and biology benefits from opportunities provided by droplet-based microfluidic systems. These systems enable the miniaturization of reactions by compartmentalizing reactions in droplets of femoliter to microliter volumes. Compartmentalization in droplets provides rapid mixing of reagents, control of the timing of reactions on timescales from milliseconds to months, control of interfacial properties, and the ability to synthesize and transport solid reagents and products. Droplet-based microfluidics can help to enhance and accelerate chemical and biochemical screening, protein crystallization, enzymatic kinetics, and assays. Moreover, the control provided by droplets in microfluidic devices can lead to new scientific methods and insights. PMID:17086584

Finite element procedures for time-dependent convection-diffusion-reaction systems

NASA Technical Reports Server (NTRS)

Tezduyar, T. E.; Park, Y. J.; Deans, H. A.

1988-01-01

New finite element procedures based on the streamline-upwind/Petrov-Galerkin formulations are developed for time-dependent convection-diffusion-reaction equations. These procedures minimize spurious oscillations for convection-dominated and reaction-dominated problems. The results obtained for representative numerical examples are accurate with minimal oscillations. As a special application problem, the single-well chemical tracer test (a procedure for measuring oil remaining in a depleted field) is simulated numerically. The results show the importance of temperature effects on the interpreted value of residual oil saturation from such tests.

Reaction Buildup of PBX Explosives JOB-9003 under Different Initiation Pressures

NASA Astrophysics Data System (ADS)

Zhang, Xu; Wang, Yan-fei; Hung, Wen-bin; Gu, Yan; Zhao, Feng; Wu, Qiang; Yu, Xin; Yu, Heng

2017-04-01

Aluminum-based embedded multiple electromagnetic particle velocity gauge technique has been developed in order to measure the shock initiation behavior of JOB-9003 explosives. In addition, another gauge element called a shock tracker has been used to monitor the progress of the shock front as a function of time, thus providing a position-time trajectory of the wave front as it moves through the explosive sample. The data are used to determine the position and time for shock to detonation transition. All the experimental results show that: the rising-up time of Al-based electromagnetic particle velocity gauge was very fast and less than 20 ns; the reaction buildup velocity profiles and the position-time for shock to detonation transition of HMX-based PBX explosive JOB-9003 with 1-8 mm depth from the origin of impact plane under different initiation pressures are obtained with high accuracy.

Detection and quantification of Renibacterium salmoninarum DNA in salmonid tissues by real-time quantitative polymerase chain reaction analysis

USGS Publications Warehouse

Chase, D.M.; Elliott, D.G.; Pascho, R.J.

2006-01-01

Renibacterium salmoninarum is an important salmonid pathogen that is difficult to culture. We developed and assessed a real-time, quantitative, polymerase chain reaction (qPCR) assay for the detection and enumeration of R. salmoninarum. The qPCR is based on TaqMan technology and amplifies a 69-base pair (bp) region of the gene encoding the major soluble antigen (MSA) of R. salmoninarum. The qPCR assay consistently detected as few as 5 R. salmoninarum cells per reaction in kidney tissue. The specificity of the qPCR was confirmed by testing the DNA extracts from a panel of microorganisms that were either common fish pathogens or reported to cause false-positive reactions in the enzyme-linked immunosorbent assay (ELISA). Kidney samples from 38 juvenile Chinook salmon (Oncorhynchus tshawytscha) in a naturally infected population were examined by real-time qPCR, a nested PCR, and ELISA, and prevalences of R. salmoninarum detected were 71, 66, and 71%, respectively. The qPCR should be a valuable tool for evaluating the R. salmoninarum infection status of salmonids.

Addressing fluorogenic real-time qPCR inhibition using the novel custom Excel file system 'FocusField2-6GallupqPCRSet-upTool-001' to attain consistently high fidelity qPCR reactions

PubMed Central

Ackermann, Mark R.

2006-01-01

The purpose of this manuscript is to discuss fluorogenic real-time quantitative polymerase chain reaction (qPCR) inhibition and to introduce/define a novel Microsoft Excel-based file system which provides a way to detect and avoid inhibition, and enables investigators to consistently design dynamically-sound, truly LOG-linear qPCR reactions very quickly. The qPCR problems this invention solves are universal to all qPCR reactions, and it performs all necessary qPCR set-up calculations in about 52 seconds (using a pentium 4 processor) for up to seven qPCR targets and seventy-two samples at a time – calculations that commonly take capable investigators days to finish. We have named this custom Excel-based file system "FocusField2-6GallupqPCRSet-upTool-001" (FF2-6-001 qPCR set-up tool), and are in the process of transforming it into professional qPCR set-up software to be made available in 2007. The current prototype is already fully functional. PMID:17033699

Particle velocity measurements of the reaction zone in nitromethane

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

Sheffield, S. A.; Engelke, R. P.; Alcon, R. R.

2002-01-01

The detonation reaction-zone length in neat, deuterated, and chemically sensitized nitromethane (NM) has been measured by using several different laser-based velocity interferometry systems. The experiments involved measuring the particle velocity history at a NM/PMMA (polymethylmethacrylate) window interface during the time a detonation in the NM interacted with the interface. Initially, Fabry-Perot interferometry was used, but, because of low time resolution (>5 ns), several different configurations of VISAR interferometry were subsequently used. Early work was done with VISARs with a time resolution of about 3 ns. By making changes to the recording system, we were able to improve this to {approx}1more » ns. Profiles measured at the NM/PMMA interface agree with the ZND theory, in that a spike ({approx}2.45 mm/{micro}s) is measured that is consistent with an extrapolated reactant NM Hugoniot matched to the PMMA window. The spike is rather sharp, followed by a rapid drop in particle velocity over a time of 5 to 10 ns; this is evidence of early fast reactions. Over about 50 ns, a much slower particle velocity decrease occurs to the assumed CJ condition - indicating a total reaction zone length of {approx}300 {micro}m. When the NM is chemically changed, such as replacing the hydrogen atoms with deuterium or chemically sensitizing with a base, some changes are observed in the early part of the reaction zone.« less

Effect of fatigue on reaction time, response time, performance time, and kick impact in taekwondo roundhouse kick.

PubMed

Sant'Ana, Jader; Franchini, Emerson; da Silva, Vinicius; Diefenthaeler, Fernando

2017-06-01

Reaction time and response time are considered important abilities and can potentially affect combat performance. This study investigated the effect of a specific fatigue protocol on reaction time, response time, performance time, and kick impact. Seven male athletes reported to the laboratory on two different days. During day one, athletes performed a specific progressive taekwondo test, and on day two, a protocol for determining reaction time, response time, performance time, and kick impact before and after a time to exhaustion test at an intensity level corresponding to the maximal kick frequency obtained during the specific progressive taekwondo test. Muscle activation from rectus femoris and kick impact of the preferred limb were assessed. No differences were observed for response time and performance time. However, kick impact decreased (43 ± 27 to 13 ± 10 g, p < 0.01) while reaction time increased (145 ± 51 to 223 ± 133 ms, p < 0.05). Moderate correlation was observed between kick impact and response time (r = 0.565; p < 0.01), and kick impact and performance time (r = 0.494; p < 0.05). Results indicate that coaches and athletes may use taekwondo training programmes on coordination-based exercises leading to improve response time and to reduce fatigue effects in order to improve technique effectiveness and enhance the possibilities of scoring in a competitive situation.

Finite-time robust passive control for a class of switched reaction-diffusion stochastic complex dynamical networks with coupling delays and impulsive control

NASA Astrophysics Data System (ADS)

Syed Ali, M.; Yogambigai, J.; Kwon, O. M.

2018-03-01

Finite-time boundedness and finite-time passivity for a class of switched stochastic complex dynamical networks (CDNs) with coupling delays, parameter uncertainties, reaction-diffusion term and impulsive control are studied. Novel finite-time synchronisation criteria are derived based on passivity theory. This paper proposes a CDN consisting of N linearly and diffusively coupled identical reaction- diffusion neural networks. By constructing of a suitable Lyapunov-Krasovskii's functional and utilisation of Jensen's inequality and Wirtinger's inequality, new finite-time passivity criteria for the networks are established in terms of linear matrix inequalities (LMIs), which can be checked numerically using the effective LMI toolbox in MATLAB. Finally, two interesting numerical examples are given to show the effectiveness of the theoretical results.

Extending the Life of Lithium-Based Rechargeable Batteries by Reaction of Lithium Dendrites with a Novel Silica Nanoparticle Sandwiched Separator

DOE PAGES

Liu, Kai; Zhuo, Denys; Lee, Hyun -Wook; ...

2016-11-22

A reaction-protective separator that slows the growth of lithium dendrites penetrating into the separator is produced by sandwiching silica nanoparticles between two polymer separators. Here, the reaction between lithium dendrites and silica nanoparticles consumes the dendrites and can extend the life of the battery by approximately five times.

On the Green's function of the partially diffusion-controlled reversible ABCD reaction for radiation chemistry codes

NASA Astrophysics Data System (ADS)

Plante, Ianik; Devroye, Luc

2015-09-01

Several computer codes simulating chemical reactions in particles systems are based on the Green's functions of the diffusion equation (GFDE). Indeed, many types of chemical systems have been simulated using the exact GFDE, which has also become the gold standard for validating other theoretical models. In this work, a simulation algorithm is presented to sample the interparticle distance for partially diffusion-controlled reversible ABCD reaction. This algorithm is considered exact for 2-particles systems, is faster than conventional look-up tables and uses only a few kilobytes of memory. The simulation results obtained with this method are compared with those obtained with the independent reaction times (IRT) method. This work is part of our effort in developing models to understand the role of chemical reactions in the radiation effects on cells and tissues and may eventually be included in event-based models of space radiation risks. However, as many reactions are of this type in biological systems, this algorithm might play a pivotal role in future simulation programs not only in radiation chemistry, but also in the simulation of biochemical networks in time and space as well.

Accelerating moderately stiff chemical kinetics in reactive-flow simulations using GPUs

NASA Astrophysics Data System (ADS)

Niemeyer, Kyle E.; Sung, Chih-Jen

2014-01-01

The chemical kinetics ODEs arising from operator-split reactive-flow simulations were solved on GPUs using explicit integration algorithms. Nonstiff chemical kinetics of a hydrogen oxidation mechanism (9 species and 38 irreversible reactions) were computed using the explicit fifth-order Runge-Kutta-Cash-Karp method, and the GPU-accelerated version performed faster than single- and six-core CPU versions by factors of 126 and 25, respectively, for 524,288 ODEs. Moderately stiff kinetics, represented with mechanisms for hydrogen/carbon-monoxide (13 species and 54 irreversible reactions) and methane (53 species and 634 irreversible reactions) oxidation, were computed using the stabilized explicit second-order Runge-Kutta-Chebyshev (RKC) algorithm. The GPU-based RKC implementation demonstrated an increase in performance of nearly 59 and 10 times, for problem sizes consisting of 262,144 ODEs and larger, than the single- and six-core CPU-based RKC algorithms using the hydrogen/carbon-monoxide mechanism. With the methane mechanism, RKC-GPU performed more than 65 and 11 times faster, for problem sizes consisting of 131,072 ODEs and larger, than the single- and six-core RKC-CPU versions, and up to 57 times faster than the six-core CPU-based implicit VODE algorithm on 65,536 ODEs. In the presence of more severe stiffness, such as ethylene oxidation (111 species and 1566 irreversible reactions), RKC-GPU performed more than 17 times faster than RKC-CPU on six cores for 32,768 ODEs and larger, and at best 4.5 times faster than VODE on six CPU cores for 65,536 ODEs. With a larger time step size, RKC-GPU performed at best 2.5 times slower than six-core VODE for 8192 ODEs and larger. Therefore, the need for developing new strategies for integrating stiff chemistry on GPUs was discussed.

A recyclable and base-free method for the synthesis of 3-iodothiophenes by the iodoheterocyclisation of 1-mercapto-3-alkyn-2-ols in ionic liquids.

PubMed

Mancuso, Raffaella; Pomelli, Christian S; Chiappe, Cinzia; Larock, Richard C; Gabriele, Bartolo

2014-01-28

The first example of an iodocyclisation reaction made recyclable by the use of an ionic liquid as the reaction medium is reported. Readily available 1-mercapto-3-alkyn-2-ols were smoothly converted into the corresponding 3-iodothiophenes (50-81% yields, 10 examples) when allowed to react with iodine (1-2 equiv.) in a proper ionic liquid, such as 1-ethyl-3-methylimidazolium ethyl sulfate (EmimEtSO4), as the solvent under mild reaction conditions (25 °C) and in the absence of an external base. The reaction medium can be recycled several times without significantly affecting the reaction outcome. Theoretical calculations have also been performed to investigate the role of the ionic liquid anion in the reaction.

Relating Derived Relations as a Model of Analogical Reasoning: Reaction Times and Event-Related Potentials

ERIC Educational Resources Information Center

Barnes-Holmes, Dermot; Regan, Donal; Barnes-Holmes, Yvonne; Commins, Sean; Walsh, Derek; Stewart, Ian; Smeets, Paul M.; Whelan, Robert; Dymond, Simon

2005-01-01

The current study aimed to test a Relational Frame Theory (RFT) model of analogical reasoning based on the relating of derived same and derived difference relations. Experiment 1 recorded reaction time measures of similar-similar (e.g., "apple is to orange as dog is to cat") versus different-different (e.g., "he is to his brother as…

Frequency and risk factors for donor reactions in an anonymous blood donor survey.

PubMed

Goldman, Mindy; Osmond, Lori; Yi, Qi-Long; Cameron-Choi, Keltie; O'Brien, Sheila F

2013-09-01

Adverse donor reactions can result in injury and decrease the likelihood of donor return. Reaction reports captured in the blood center's database provide an incomplete picture of reaction rates and risk factors. We performed an anonymous survey, mailed to 40,000 donors in 2008, including questions about symptoms, height, weight, sex, and donation status. Reaction rates were compared to those recorded in our database. Possible risk factors were assessed for various reactions. The response rate was 45.5%. A total of 32% of first-time and 14% of repeat donors reported having any adverse symptom, most frequently bruising (84.9 per 1000 donors) or feeling faint or weak (66.2 per 1000). Faint reactions were two to eight times higher than reported in our database, although direct comparison was difficult. Younger age, female sex, and first-time donation status were risk factors for systemic and arm symptoms. In females, low estimated blood volume (EBV) was a risk factor for systemic symptoms. Only 51% of donors who consulted an outside physician also called Canadian Blood Services. A total of 10% of first-time donors with reactions found adverse effects information inadequate. This study allowed us to collect more information about adverse reactions, including minor symptoms and delayed reactions. Based on our findings of the risk factors and frequency of adverse reactions, we are implementing more stringent EBV criteria for younger donors and providing more detailed information to donors about possible adverse effects and their management. © 2012 American Association of Blood Banks.

Synthesis of soybean oil-based thiol oligomers.

PubMed

Wu, Jennifer F; Fernando, Shashi; Weerasinghe, Dimuthu; Chen, Zhigang; Webster, Dean C

2011-08-22

Industrial grade soybean oil (SBO) and thiols were reacted to generate thiol-functionalized oligomers via a thermal, free radical initiated thiol-ene reaction between the SBO double bond moieties and the thiol functional groups. The effect of the reaction conditions, including thiol concentration, catalyst loading level, reaction time, and atmosphere, on the molecular weight and the conversion to the resultant soy-thiols were examined in a combinatorial high-throughput fashion using parallel synthesis, combinatorial FTIR, and rapid gel permeation chromatography (GPC). High thiol functionality and concentration, high thermal free radical catalyst concentration, long reaction time, and the use of a nitrogen reaction atmosphere were found to favor fast consumption of the SBO, and produced high molecular weight products. The thiol conversion during the reaction was inversely affected by a high thiol concentration, but was favored by a long reaction time and an air reaction atmosphere. These experimental observations were explained by the initial low affinity of the SBO and thiol, and the improved affinity between the generated soy-thiol oligomers and unreacted SBO during the reaction. The synthesized soy-thiol oligomers can be used for renewable thiol-ene UV curable materials and high molecular solids and thiourethane thermal cure materials. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Techniques used to study the DNA polymerase reaction pathway

PubMed Central

Joyce, Catherine M.

2009-01-01

Summary A minimal reaction pathway for DNA polymerases was established over 20 years ago using chemical quench methods. Since that time there has been considerable interest in noncovalent steps in the reaction pathway, conformational changes involving the polymerase or its DNA substrate that may play a role in substrate specificity. Fluorescence-based assays have been devised in order to study these conformational transitions and the results obtained have added new detail to the reaction pathway. PMID:19665596

A Catalyst-Free Amination of Functional Organolithium Reagents by Flow Chemistry.

PubMed

Kim, Heejin; Yonekura, Yuya; Yoshida, Jun-Ichi

2018-04-03

Reported is the electrophilic amination of functional organolithium intermediates with well-designed aminating reagents under mild reaction conditions using flow microreactors. The aminating reagents were optimized to achieve efficient C-N bond formation without using any catalyst. The electrophilic amination reactions of functionalized aryllithiums were successfully conducted under mild reaction conditions, within 1 minute, by using flow microreactors. The aminating reagent was also prepared by the flow method. Based on stopped-flow NMR analysis, the reaction time for the preparation of the aminating reagent was quickly optimized without the necessity of work-up. Integrated one-flow synthesis consisting of the generation of an aryllithium, the preparation of an aminating reagent, and their combined reaction was successfully achieved to give the desired amine within 5 minutes of total reaction time. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid detection of highly pathogenic porcine reproductive and respiratory syndrome virus by a fluorescent probe-based isothermal recombinase polymerase amplification assay.

PubMed

Yang, Yang; Qin, Xiaodong; Sun, Yingjun; Chen, Ting; Zhang, Zhidong

2016-12-01

A novel fluorescent probe-based real-time reverse transcription recombinase polymerase amplification (real-time RT-RPA) assay was developed for rapid detection of highly pathogenic type 2 porcine reproductive and respiratory syndrome virus (HP-PRRSV). The sensitivity analysis showed that the detection limit of RPA was 70 copies of HP-PRRSV RNA/reaction. The real-time RT-RPA highly specific amplified HP-PRRSV with no cross-reaction with classic PRRSV, classic swine fever virus, pseudorabies virus, and foot-and-mouth disease virus. Assessment with 125 clinical samples showed that the developed real-time RT-RPA assay was well correlated with real-time RT-qPCR assays for detection of HP-PRRSV. These results suggest that the developed real-time RT-RPA assay is suitable for rapid detection of HP-PRRSV.

Wang-Landau Reaction Ensemble Method: Simulation of Weak Polyelectrolytes and General Acid-Base Reactions.

PubMed

Landsgesell, Jonas; Holm, Christian; Smiatek, Jens

2017-02-14

We present a novel method for the study of weak polyelectrolytes and general acid-base reactions in molecular dynamics and Monte Carlo simulations. The approach combines the advantages of the reaction ensemble and the Wang-Landau sampling method. Deprotonation and protonation reactions are simulated explicitly with the help of the reaction ensemble method, while the accurate sampling of the corresponding phase space is achieved by the Wang-Landau approach. The combination of both techniques provides a sufficient statistical accuracy such that meaningful estimates for the density of states and the partition sum can be obtained. With regard to these estimates, several thermodynamic observables like the heat capacity or reaction free energies can be calculated. We demonstrate that the computation times for the calculation of titration curves with a high statistical accuracy can be significantly decreased when compared to the original reaction ensemble method. The applicability of our approach is validated by the study of weak polyelectrolytes and their thermodynamic properties.

Flash chemistry: flow chemistry that cannot be done in batch.

PubMed

Yoshida, Jun-ichi; Takahashi, Yusuke; Nagaki, Aiichiro

2013-11-04

Flash chemistry based on high-resolution reaction time control using flow microreactors enables chemical reactions that cannot be done in batch and serves as a powerful tool for laboratory synthesis of organic compounds and for production in chemical and pharmaceutical industries.

A Flight-Calibrated Methodology for Determination of Cassini Thruster On-Times for Reaction Wheel Biases

NASA Technical Reports Server (NTRS)

Sarani, Siamak

2010-01-01

This paper describes a methodology for accurate and flight-calibrated determination of the on-times of the Cassini spacecraft Reaction Control System (RCS) thrusters, without any form of dynamic simulation, for the reaction wheel biases. The hydrazine usage and the delta V vector in body frame are also computed from the respective thruster on-times. The Cassini spacecraft, the largest and most complex interplanetary spacecraft ever built, continues to undertake ambitious and unique scientific observations of planet Saturn, Titan, Enceladus, and other moons of Saturn. In order to maintain a stable attitude during the course of its mission, this three-axis stabilized spacecraft uses two different control systems: the RCS and the reaction wheel assembly control system. The RCS is used to execute a commanded spacecraft slew, to maintain three-axis attitude control, control spacecraft's attitude while performing science observations with coarse pointing requirements, e.g. during targeted low-altitude Titan and Enceladus flybys, bias the momentum of reaction wheels, and to perform RCS-based orbit trim maneuvers. The use of RCS often imparts undesired delta V on the spacecraft. The Cassini navigation team requires accurate predictions of the delta V in spacecraft coordinates and inertial frame resulting from slews using RCS thrusters and more importantly from reaction wheel bias events. It is crucial for the Cassini spacecraft attitude control and navigation teams to be able to, quickly but accurately, predict the hydrazine usage and delta V for various reaction wheel bias events without actually having to spend time and resources simulating the event in flight software-based dynamic simulation or hardware-in-the-loop simulation environments. The methodology described in this paper, and the ground software developed thereof, are designed to provide just that. This methodology assumes a priori knowledge of thrust magnitudes and thruster pulse rise and tail-off time constants for eight individual attitude control thrusters, the spacecraft's wet mass and its center of mass location, and a few other key parameters.

Modeling marine oily wastewater treatment by a probabilistic agent-based approach.

PubMed

Jing, Liang; Chen, Bing; Zhang, Baiyu; Ye, Xudong

2018-02-01

This study developed a novel probabilistic agent-based approach for modeling of marine oily wastewater treatment processes. It begins first by constructing a probability-based agent simulation model, followed by a global sensitivity analysis and a genetic algorithm-based calibration. The proposed modeling approach was tested through a case study of the removal of naphthalene from marine oily wastewater using UV irradiation. The removal of naphthalene was described by an agent-based simulation model using 8 types of agents and 11 reactions. Each reaction was governed by a probability parameter to determine its occurrence. The modeling results showed that the root mean square errors between modeled and observed removal rates were 8.73 and 11.03% for calibration and validation runs, respectively. Reaction competition was analyzed by comparing agent-based reaction probabilities, while agents' heterogeneity was visualized by plotting their real-time spatial distribution, showing a strong potential for reactor design and process optimization. Copyright © 2017 Elsevier Ltd. All rights reserved.

Real-Time Reverse Transcription–Polymerase Chain Reaction Assay for SARS-associated Coronavirus

PubMed Central

Emery, Shannon L.; Bowen, Michael D.; Newton, Bruce R.; Winchell, Jonas M.; Meyer, Richard F.; Tong, Suxiang; Cook, Byron T.; Holloway, Brian P.; McCaustland, Karen A.; Rota, Paul A.; Bankamp, Bettina; Lowe, Luis E.; Ksiazek, Tom G.; Bellini, William J.; Anderson, Larry J.

2004-01-01

A real-time reverse transcription–polymerase chain reaction (RT-PCR) assay was developed to rapidly detect the severe acute respiratory syndrome–associated coronavirus (SARS-CoV). The assay, based on multiple primer and probe sets located in different regions of the SARS-CoV genome, could discriminate SARS-CoV from other human and animal coronaviruses with a potential detection limit of <10 genomic copies per reaction. The real-time RT-PCR assay was more sensitive than a conventional RT-PCR assay or culture isolation and proved suitable to detect SARS-CoV in clinical specimens. Application of this assay will aid in diagnosing SARS-CoV infection. PMID:15030703

A comparison of the bromination dynamics of pitch-based and vapor-grown graphite fibers

NASA Technical Reports Server (NTRS)

Gaier, J. R.

1986-01-01

The electrical resistance of pitch based P-100 fibers and experimental organic vapor grown fibers was recorded in-situ during bromination and subsequent exposure to ambient laboratory air. The results indicate that the bromination and debromination reactions proceed much slower for vapor grown fibers than for pitch based. While this may be due in part to the larger diameter of the vapor grown fibers, the majority of the effect can probably be attributed to the differences in graphene plane orientation between the fiber types. Although the reactions are slower in the vapor grown than in the pitch based fibers, the extent of reaction as measured by the change in electrical resistance is essentially the same, with comparable (or larger) decreases in resistivity. The bromination reaction proceeds with one or more plateaus in the resistance versus time curves, which suggests staging and strengthens the argument that these fibers produce true intercalation compounds.

Incorporating extrinsic noise into the stochastic simulation of biochemical reactions: A comparison of approaches

NASA Astrophysics Data System (ADS)

Thanh, Vo Hong; Marchetti, Luca; Reali, Federico; Priami, Corrado

2018-02-01

The stochastic simulation algorithm (SSA) has been widely used for simulating biochemical reaction networks. SSA is able to capture the inherently intrinsic noise of the biological system, which is due to the discreteness of species population and to the randomness of their reciprocal interactions. However, SSA does not consider other sources of heterogeneity in biochemical reaction systems, which are referred to as extrinsic noise. Here, we extend two simulation approaches, namely, the integration-based method and the rejection-based method, to take extrinsic noise into account by allowing the reaction propensities to vary in time and state dependent manner. For both methods, new efficient implementations are introduced and their efficiency and applicability to biological models are investigated. Our numerical results suggest that the rejection-based method performs better than the integration-based method when the extrinsic noise is considered.

No evidence of persisting measles virus in peripheral blood mononuclear cells from children with autism spectrum disorder.

PubMed

D'Souza, Yasmin; Fombonne, Eric; Ward, Brian J

2006-10-01

Despite epidemiologic evidence to the contrary, claims of an association between measles-mumps-rubella vaccination and the development of autism have persisted. Such claims are based primarily on the identification of measles virus nucleic acids in tissues and body fluids by polymerase chain reaction. We sought to determine whether measles virus nucleic acids persist in children with autism spectrum disorder compared with control children. Peripheral blood mononuclear cells were isolated from 54 children with autism spectrum disorder and 34 developmentally normal children, and up to 4 real-time polymerase chain reaction assays and 2 nested polymerase chain reaction assays were performed. These assays targeted the nucleoprotein, fusion, and hemagglutinin genes of measles virus using previously published primer pairs with detection by SYBR green I. Our own real-time assay targeted the fusion gene using novel primers and an internal fluorescent probe. Positive reactions were evaluated rigorously, and amplicons were sequenced. Finally, anti-measles antibody titers were measured by enzyme immunoassay. The real-time assays based on previously published primers gave rise to a large number of positive reactions in both autism spectrum disorder and control samples. Almost all of the positive reactions in these assays were eliminated by evaluation of melting curves and amplicon band size. The amplicons for the remaining positive reactions were cloned and sequenced. No sample from either autism spectrum disorder or control groups was found to contain nucleic acids from any measles virus gene. In the nested polymerase chain reaction and in-house assays, none of the samples yielded positive results. Furthermore, there was no difference in anti-measles antibody titers between the autism and control groups. There is no evidence of measles virus persistence in the peripheral blood mononuclear cells of children with autism spectrum disorder.

A redox-mediated chromogenic reaction and application in immunoassay.

PubMed

Yu, Ru-Jia; Ma, Wei; Peng, Mao-Pan; Bai, Zhi-Shan; Long, Yi-Tao

2016-08-31

A novel redox-mediated chromogenic reaction was demonstrated based on the reaction between HAuCl4 and 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), which generate various color responses from red to green in the resulting solutions. Various redox substance could be used to mediate the reaction and trigger a distinct color response. We established a sensitive hydrogen peroxide colorimetric sensor based on the redox-mediated chromogenic reaction and depicted the application both in detection of enzyme and in an immunoassay. Combining the traditional chromogenic reagent with gold nanoparticles, our assay has the advantage in short response time (within three minutes), high sensitivity (10(-12) g mL(-1) for HBsAg) and stability. Copyright © 2016. Published by Elsevier B.V.

A molecular dynamics study of intramolecular proton transfer reaction of malonaldehyde in solutions based upon mixed quantum-classical approximation. I. Proton transfer reaction in water

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

Yamada, Atsushi; Kojima, Hidekazu; Okazaki, Susumu, E-mail: okazaki@apchem.nagoya-u.ac.jp

2014-08-28

In order to investigate proton transfer reaction in solution, mixed quantum-classical molecular dynamics calculations have been carried out based on our previously proposed quantum equation of motion for the reacting system [A. Yamada and S. Okazaki, J. Chem. Phys. 128, 044507 (2008)]. Surface hopping method was applied to describe forces acting on the solvent classical degrees of freedom. In a series of our studies, quantum and solvent effects on the reaction dynamics in solutions have been analysed in detail. Here, we report our mixed quantum-classical molecular dynamics calculations for intramolecular proton transfer of malonaldehyde in water. Thermally activated proton transfermore » process, i.e., vibrational excitation in the reactant state followed by transition to the product state and vibrational relaxation in the product state, as well as tunneling reaction can be described by solving the equation of motion. Zero point energy is, of course, included, too. The quantum simulation in water has been compared with the fully classical one and the wave packet calculation in vacuum. The calculated quantum reaction rate in water was 0.70 ps{sup −1}, which is about 2.5 times faster than that in vacuum, 0.27 ps{sup −1}. This indicates that the solvent water accelerates the reaction. Further, the quantum calculation resulted in the reaction rate about 2 times faster than the fully classical calculation, which indicates that quantum effect enhances the reaction rate, too. Contribution from three reaction mechanisms, i.e., tunneling, thermal activation, and barrier vanishing reactions, is 33:46:21 in the mixed quantum-classical calculations. This clearly shows that the tunneling effect is important in the reaction.« less

Novel particle tracking algorithm based on the Random Sample Consensus Model for the Active Target Time Projection Chamber (AT-TPC)

NASA Astrophysics Data System (ADS)

Ayyad, Yassid; Mittig, Wolfgang; Bazin, Daniel; Beceiro-Novo, Saul; Cortesi, Marco

2018-02-01

The three-dimensional reconstruction of particle tracks in a time projection chamber is a challenging task that requires advanced classification and fitting algorithms. In this work, we have developed and implemented a novel algorithm based on the Random Sample Consensus Model (RANSAC). The RANSAC is used to classify tracks including pile-up, to remove uncorrelated noise hits, as well as to reconstruct the vertex of the reaction. The algorithm, developed within the Active Target Time Projection Chamber (AT-TPC) framework, was tested and validated by analyzing the 4He+4He reaction. Results, performance and quality of the proposed algorithm are presented and discussed in detail.

Organic radicals for the enhancement of oxygen reduction reaction in Li-O2 batteries.

PubMed

Tesio, A Y; Blasi, D; Olivares-Marín, M; Ratera, I; Tonti, D; Veciana, J

2015-12-25

We examine for the first time the ability of inert carbon free-radicals as soluble redox mediators to catalyze and enhance the oxygen reduction reaction in a (TEGDME)-based electrolyte. We demonstrate that the tris(2,4,6-trichlorophenyl)methyl (TTM) radical is capable of chemically favoring the oxygen reduction reaction improving significantly the Li-O2 battery performance.

Worldwide withdrawal of medicinal products because of adverse drug reactions: a systematic review and analysis.

PubMed

Onakpoya, Igho J; Heneghan, Carl J; Aronson, Jeffrey K

2016-07-01

We have systematically identified medicinal products withdrawn worldwide because of adverse drug reactions, assessed the level of evidence used for making the withdrawal decisions, and explored the patterns of withdrawals over time. We searched PubMed, the WHO database of withdrawn products, and selected texts. We included products that were withdrawn after launch from 1950 onwards, excluding non-human and over-the-counter medicines. We assessed the levels of evidence on which withdrawals were based using the Oxford Center for Evidence Based Medicine Levels of Evidence. Of 353 medicinal products withdrawn from any country, only 40 were withdrawn worldwide. Anecdotal reports were cited as evidence for withdrawal in 30 (75%) and deaths occurred in 27 (68%). Hepatic, cardiac, and nervous system toxicity accounted for over 60% of withdrawals. In 28 cases, the first withdrawal was initiated by the manufacturer. The median interval between the first report of an adverse drug reaction that led to withdrawal and the first withdrawal was 1 year (range 0-43 years). Worldwide withdrawals occurred within 1 year after the first withdrawal in any country. In conclusion, the time it takes for drugs to be withdrawn worldwide after reports of adverse drug reactions has shortened over time. However, there are inconsistencies in current withdrawal procedures when adverse drug reactions are suspected. A uniform method for establishing worldwide withdrawal of approved medicinal products when adverse drug reactions are suspected should be developed, to facilitate global withdrawals. Rapid synthesis of the evidence on harms should be a priority when serious adverse reactions are suspected.

Stochastic simulation of reaction-diffusion systems: A fluctuating-hydrodynamics approach

NASA Astrophysics Data System (ADS)

Kim, Changho; Nonaka, Andy; Bell, John B.; Garcia, Alejandro L.; Donev, Aleksandar

2017-03-01

We develop numerical methods for stochastic reaction-diffusion systems based on approaches used for fluctuating hydrodynamics (FHD). For hydrodynamic systems, the FHD formulation is formally described by stochastic partial differential equations (SPDEs). In the reaction-diffusion systems we consider, our model becomes similar to the reaction-diffusion master equation (RDME) description when our SPDEs are spatially discretized and reactions are modeled as a source term having Poisson fluctuations. However, unlike the RDME, which becomes prohibitively expensive for an increasing number of molecules, our FHD-based description naturally extends from the regime where fluctuations are strong, i.e., each mesoscopic cell has few (reactive) molecules, to regimes with moderate or weak fluctuations, and ultimately to the deterministic limit. By treating diffusion implicitly, we avoid the severe restriction on time step size that limits all methods based on explicit treatments of diffusion and construct numerical methods that are more efficient than RDME methods, without compromising accuracy. Guided by an analysis of the accuracy of the distribution of steady-state fluctuations for the linearized reaction-diffusion model, we construct several two-stage (predictor-corrector) schemes, where diffusion is treated using a stochastic Crank-Nicolson method, and reactions are handled by the stochastic simulation algorithm of Gillespie or a weakly second-order tau leaping method. We find that an implicit midpoint tau leaping scheme attains second-order weak accuracy in the linearized setting and gives an accurate and stable structure factor for a time step size of an order of magnitude larger than the hopping time scale of diffusing molecules. We study the numerical accuracy of our methods for the Schlögl reaction-diffusion model both in and out of thermodynamic equilibrium. We demonstrate and quantify the importance of thermodynamic fluctuations to the formation of a two-dimensional Turing-like pattern and examine the effect of fluctuations on three-dimensional chemical front propagation. By comparing stochastic simulations to deterministic reaction-diffusion simulations, we show that fluctuations accelerate pattern formation in spatially homogeneous systems and lead to a qualitatively different disordered pattern behind a traveling wave.

Stochastic simulation of reaction-diffusion systems: A fluctuating-hydrodynamics approach

DOE PAGES

Kim, Changho; Nonaka, Andy; Bell, John B.; ...

2017-03-24

Here, we develop numerical methods for stochastic reaction-diffusion systems based on approaches used for fluctuating hydrodynamics (FHD). For hydrodynamic systems, the FHD formulation is formally described by stochastic partial differential equations (SPDEs). In the reaction-diffusion systems we consider, our model becomes similar to the reaction-diffusion master equation (RDME) description when our SPDEs are spatially discretized and reactions are modeled as a source term having Poisson fluctuations. However, unlike the RDME, which becomes prohibitively expensive for an increasing number of molecules, our FHD-based description naturally extends from the regime where fluctuations are strong, i.e., each mesoscopic cell has few (reactive) molecules,more » to regimes with moderate or weak fluctuations, and ultimately to the deterministic limit. By treating diffusion implicitly, we avoid the severe restriction on time step size that limits all methods based on explicit treatments of diffusion and construct numerical methods that are more efficient than RDME methods, without compromising accuracy. Guided by an analysis of the accuracy of the distribution of steady-state fluctuations for the linearized reaction-diffusion model, we construct several two-stage (predictor-corrector) schemes, where diffusion is treated using a stochastic Crank-Nicolson method, and reactions are handled by the stochastic simulation algorithm of Gillespie or a weakly second-order tau leaping method. We find that an implicit midpoint tau leaping scheme attains second-order weak accuracy in the linearized setting and gives an accurate and stable structure factor for a time step size of an order of magnitude larger than the hopping time scale of diffusing molecules. We study the numerical accuracy of our methods for the Schlögl reaction-diffusion model both in and out of thermodynamic equilibrium. We demonstrate and quantify the importance of thermodynamic fluctuations to the formation of a two-dimensional Turing-like pattern and examine the effect of fluctuations on three-dimensional chemical front propagation. Furthermore, by comparing stochastic simulations to deterministic reaction-diffusion simulations, we show that fluctuations accelerate pattern formation in spatially homogeneous systems and lead to a qualitatively different disordered pattern behind a traveling wave.« less

Real time monitoring of accelerated chemical reactions by ultrasonication-assisted spray ionization mass spectrometry.

PubMed

Lin, Shu-Hsuan; Lo, Ta-Ju; Kuo, Fang-Yin; Chen, Yu-Chie

2014-01-01

Ultrasonication has been used to accelerate chemical reactions. It would be ideal if ultrasonication-assisted chemical reactions could be monitored by suitable detection tools such as mass spectrometry in real time. It would be helpful to clarify reaction intermediates/products and to have a better understanding of reaction mechanism. In this work, we developed a system for ultrasonication-assisted spray ionization mass spectrometry (UASI-MS) with an ~1.7 MHz ultrasonic transducer to monitor chemical reactions in real time. We demonstrated that simply depositing a sample solution on the MHz-based ultrasonic transducer, which was placed in front of the orifice of a mass spectrometer, the analyte signals can be readily detected by the mass spectrometer. Singly and multiply charged ions from small and large molecules, respectively, can be observed in the UASI mass spectra. Furthermore, the ultrasonic transducer used in the UASI setup accelerates the chemical reactions while being monitored via UASI-MS. The feasibility of using this approach for real-time acceleration/monitoring of chemical reactions was demonstrated. The reactions of Girard T reagent and hydroxylamine with steroids were used as the model reactions. Upon the deposition of reactant solutions on the ultrasonic transducer, the intermediate/product ions are readily generated and instantaneously monitored using MS within 1 s. Additionally, we also showed the possibility of using this reactive UASI-MS approach to assist the confirmation of trace steroids from complex urine samples by monitoring the generation of the product ions. Copyright © 2014 John Wiley & Sons, Ltd.

Evaluation of Different PCR-Based Assays and LAMP Method for Rapid Detection of Phytophthora infestans by Targeting the Ypt1 Gene

PubMed Central

Khan, Mehran; Li, Benjin; Jiang, Yue; Weng, Qiyong; Chen, Qinghe

2017-01-01

Late blight, caused by the oomycete Phytophthora infestans, is one of the most devastating diseases affecting potato and tomato worldwide. Early diagnosis of the P. infestans pathogen causing late blight should be the top priority for addressing disease epidemics and management. In this study, we performed a loop-mediated isothermal amplification (LAMP) assay, conventional polymerase chain reaction (PCR), nested PCR, and real-time PCR to verify and compare the sensitivity and specificity of the reaction based on the Ypt1 (Ras-related protein) gene of P. infestans. In comparison with the PCR-based assays, the LAMP technique led to higher specificity and sensitivity, using uncomplicated equipment with an equivalent time frame. All 43 P. infestans isolates, yielded positive detection results using LAMP assay showing no cross reaction with other Phytophthora spp., oomycetes or fungal pathogens. The LAMP assay yielded the lowest detectable DNA concentration (1.28 × 10-4 ng μL-1), being 10 times more sensitive than nested PCR (1.28 × 10-3 ng μL-1), 100 times more sensitive than real-time PCR (1.28 × 10-2 ng μL-1) and 103 times more sensitive than the conventional PCR assay (1.28 × 10-1 ng μL-1). In the field experiment, the LAMP assay outperformed the other tests by amplifying only diseased tissues (leaf and stem), and showing no positive reaction in healthy tissues. Overall, the LAMP assay developed in this study provides a specific, sensitive, simple, and effective visual method for detection of the P. infestans pathogen, and is therefore suitable for application in early prediction of the disease to reduce the risk of epidemics. PMID:29051751

Evaluation of Different PCR-Based Assays and LAMP Method for Rapid Detection of Phytophthora infestans by Targeting the Ypt1 Gene.

PubMed

Khan, Mehran; Li, Benjin; Jiang, Yue; Weng, Qiyong; Chen, Qinghe

2017-01-01

Late blight, caused by the oomycete Phytophthora infestans , is one of the most devastating diseases affecting potato and tomato worldwide. Early diagnosis of the P. infestans pathogen causing late blight should be the top priority for addressing disease epidemics and management. In this study, we performed a loop-mediated isothermal amplification (LAMP) assay, conventional polymerase chain reaction (PCR), nested PCR, and real-time PCR to verify and compare the sensitivity and specificity of the reaction based on the Ypt1 (Ras-related protein) gene of P. infestans. In comparison with the PCR-based assays, the LAMP technique led to higher specificity and sensitivity, using uncomplicated equipment with an equivalent time frame. All 43 P. infestans isolates, yielded positive detection results using LAMP assay showing no cross reaction with other Phytophthora spp., oomycetes or fungal pathogens. The LAMP assay yielded the lowest detectable DNA concentration (1.28 × 10 -4 ng μL -1 ), being 10 times more sensitive than nested PCR (1.28 × 10 -3 ng μL -1 ), 100 times more sensitive than real-time PCR (1.28 × 10 -2 ng μL -1 ) and 10 3 times more sensitive than the conventional PCR assay (1.28 × 10 -1 ng μL -1 ). In the field experiment, the LAMP assay outperformed the other tests by amplifying only diseased tissues (leaf and stem), and showing no positive reaction in healthy tissues. Overall, the LAMP assay developed in this study provides a specific, sensitive, simple, and effective visual method for detection of the P. infestans pathogen, and is therefore suitable for application in early prediction of the disease to reduce the risk of epidemics.

Vaccine allergy.

PubMed

Caubet, Jean-Christoph; Ponvert, Claude

2014-08-01

Overdiagnosis of vaccine allergy is considered a major public health problem. This article discusses the different types of allergic reactions after immunization based on the timing (immediate vs nonimmediate) and the extent of the reaction (local vs systemic). The vaccine components potentially responsible for an allergic reaction are discussed, as well as the management of patients with a history of reaction to a specific vaccine and those with a history of allergy to one of the vaccine components. Copyright © 2014 Elsevier Inc. All rights reserved.

Control of Nitrogen Dioxide in Stack Emission by Reaction with Ammonia

NASA Technical Reports Server (NTRS)

Metzler, A. J.; Stevenson, E. F.

1970-01-01

The development of an acid base gas-phase reaction system which utilizes anhydrous ammonia as the reactant to remove nitrogen dioxide from hydrazine-nitrogen tetroxide rocket combustion exhaust is reported. This reaction reduced NO2 levels in exhaust emissions so that the resulting stack emission is completely white instead of the earlier observed typical reddish-brown coloration. Preliminary analyses indicate the importance of reaction time and ammonia concentration on removal efficiency and elimination of the health hazard to individuals with respiratory problems.

Webcam camera as a detector for a simple lab-on-chip time based approach.

PubMed

Wongwilai, Wasin; Lapanantnoppakhun, Somchai; Grudpan, Supara; Grudpan, Kate

2010-05-15

A modification of a webcam camera for use as a small and low cost detector was demonstrated with a simple lab-on-chip reactor. Real time continuous monitoring of the reaction zone could be done. Acid-base neutralization with phenolphthalein indicator was used as a model reaction. The fading of pink color of the indicator when the acidic solution diffused into the basic solution zone was recorded as the change of red, blue and green colors (%RBG.) The change was related to acid concentration. A low cost portable semi-automation analysis system was achieved.

Cumulative Significance of Hyporheic Exchange and Biogeochemical Processing in River Networks

NASA Astrophysics Data System (ADS)

Harvey, J. W.; Gomez-Velez, J. D.

2014-12-01

Biogeochemical reactions in rivers that decrease excessive loads of nutrients, metals, organic compounds, etc. are enhanced by hydrologic interactions with microbially and geochemically active sediments of the hyporheic zone. The significance of reactions in individual hyporheic flow paths has been shown to be controlled by the contact time between river water and sediment and the intrinsic reaction rate in the sediment. However, little is known about how the cumulative effects of hyporheic processing in large river basins. We used the river network model NEXSS (Gomez-Velez and Harvey, submitted) to simulate hyporheic exchange through synthetic river networks based on the best available models of network topology, hydraulic geometry and scaling of geomorphic features, grain size, hydraulic conductivity, and intrinsic reaction rates of nutrients and metals in river sediment. The dimensionless reaction significance factor, RSF (Harvey et al., 2013) was used to quantify the cumulative removal fraction of a reactive solute by hyporheic processing. SF scales reaction progress in a single pass through the hyporheic zone with the proportion of stream discharge passing through the hyporheic zone for a specified distance. Reaction progress is optimal where the intrinsic reaction timescale in sediment matches the residence time of hyporheic flow and is less efficient in longer residence time hyporheic flow as a result of the decreasing proportion of river flow that is processed by longer residence time hyporheic flow paths. In contrast, higher fluxes through short residence time hyporheic flow paths may be inefficient because of the repeated surface-subsurface exchanges required to complete the reaction. Using NEXSS we found that reaction efficiency may be high in both small streams and large rivers, although for different reasons. In small streams reaction progress generally is dominated by faster pathways of vertical exchange beneath submerged bedforms. Slower exchange beneath meandering river banks mainly has importance only in large rivers. For solutes entering networks in proportion to water inputs it is the lower order streams that tend to dominate cumulative reaction progress.

Wavelet-based surrogate time series for multiscale simulation of heterogeneous catalysis

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

Savara, Aditya Ashi; Daw, C. Stuart; Xiong, Qingang

We propose a wavelet-based scheme that encodes the essential dynamics of discrete microscale surface reactions in a form that can be coupled with continuum macroscale flow simulations with high computational efficiency. This makes it possible to simulate the dynamic behavior of reactor-scale heterogeneous catalysis without requiring detailed concurrent simulations at both the surface and continuum scales using different models. Our scheme is based on the application of wavelet-based surrogate time series that encodes the essential temporal and/or spatial fine-scale dynamics at the catalyst surface. The encoded dynamics are then used to generate statistically equivalent, randomized surrogate time series, which canmore » be linked to the continuum scale simulation. As a result, we illustrate an application of this approach using two different kinetic Monte Carlo simulations with different characteristic behaviors typical for heterogeneous chemical reactions.« less

Wavelet-based surrogate time series for multiscale simulation of heterogeneous catalysis

DOE PAGES

Savara, Aditya Ashi; Daw, C. Stuart; Xiong, Qingang; ...

2016-01-28

We propose a wavelet-based scheme that encodes the essential dynamics of discrete microscale surface reactions in a form that can be coupled with continuum macroscale flow simulations with high computational efficiency. This makes it possible to simulate the dynamic behavior of reactor-scale heterogeneous catalysis without requiring detailed concurrent simulations at both the surface and continuum scales using different models. Our scheme is based on the application of wavelet-based surrogate time series that encodes the essential temporal and/or spatial fine-scale dynamics at the catalyst surface. The encoded dynamics are then used to generate statistically equivalent, randomized surrogate time series, which canmore » be linked to the continuum scale simulation. As a result, we illustrate an application of this approach using two different kinetic Monte Carlo simulations with different characteristic behaviors typical for heterogeneous chemical reactions.« less

Reconstructing biochemical pathways from time course data.

PubMed

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

2007-03-01

Time series data on biochemical reactions reveal transient behavior, away from chemical equilibrium, and contain information on the dynamic interactions among reacting components. However, this information can be difficult to extract using conventional analysis techniques. We present a new method to infer biochemical pathway mechanisms from time course data using a global nonlinear modeling technique to identify the elementary reaction steps which constitute the pathway. The method involves the generation of a complete dictionary of polynomial basis functions based on the law of mass action. Using these basis functions, there are two approaches to model construction, namely the general to specific and the specific to general approach. We demonstrate that our new methodology reconstructs the chemical reaction steps and connectivity of the glycolytic pathway of Lactococcus lactis from time course experimental data.

Fabrication Method Study of ZnO Nanocoated Cellulose Film and Its Piezoelectric Property

PubMed Central

Ko, Hyun-U; Kim, Hyun Chan; Kim, Jung Woong; Zhai, Lindong; Kim, Jaehwan

2017-01-01

Recently, a cellulose-based composite material with a thin ZnO nanolayer—namely, ZnO nanocoated cellulose film (ZONCE)—was fabricated to increase its piezoelectric charge constant. However, the fabrication method has limitations to its application in mass production. In this paper, a hydrothermal synthesis method suitable for the mass production of ZONCE (HZONCE) is proposed. A simple hydrothermal synthesis which includes a hydrothermal reaction is used for the production, and the reaction time is controlled. To improve the piezoelectric charge constant, the hydrothermal reaction is conducted twice. HZONCE fabricated by twice-hydrothermal reaction shows approximately 1.6-times improved piezoelectric charge constant compared to HZONCE fabricated by single hydrothermal reaction. Since the fabricated HZONCE has high transparency, dielectric constant, and piezoelectric constant, the proposed method can be applied for continuous mass production. PMID:28772971

Modeling and simulation of pressure waves generated by nano-thermite reactions

NASA Astrophysics Data System (ADS)

Martirosyan, Karen S.; Zyskin, Maxim; Jenkins, Charles M.; (Yuki) Horie, Yasuyuki

2012-11-01

This paper reports the modeling of pressure waves from the explosive reaction of nano-thermites consisting of mixtures of nanosized aluminum and oxidizer granules. Such nanostructured thermites have higher energy density (up to 26 kJ/cm3) and can generate a transient pressure pulse four times larger than that from trinitrotoluene (TNT) based on volume equivalence. A plausible explanation for the high pressure generation is that the reaction times are much shorter than the time for a shock wave to propagate away from the reagents region so that all the reaction energy is dumped into the gaseous products almost instantaneously and thereby a strong shock wave is generated. The goal of the modeling is to characterize the gas dynamic behavior for thermite reactions in a cylindrical reaction chamber and to model the experimentally measured pressure histories. To simplify the details of the initial stage of the explosive reaction, it is assumed that the reaction generates a one dimensional shock wave into an air-filled cylinder and propagates down the tube in a self-similar mode. Experimental data for Al/Bi2O3 mixtures were used to validate the model with attention focused on the ratio of specific heats and the drag coefficient. Model predictions are in good agreement with the measured pressure histories.

Controlling the magic and normal sizes of white CdSe quantum dots

NASA Astrophysics Data System (ADS)

Su, Yu-Sheng; Chung, Shu-Ru

2017-08-01

In this study, we have demonstrated a facile chemical route to prepare CdSe QDs with white light emission, and the performance of white CdSe-based white light emitting diode (WLED) is also exploded. An organic oleic acid (OA) is used to form Cd-OA complex first and hexadecylamine (HDA) and 1-octadecene (ODE) is used as surfactants. Meanwhile, by varying the reaction time from 1 s to 60 min, CdSe QDs with white light can be obtained. The result shows that the luminescence spectra compose two obvious emission peaks and entire visible light from 400 to 700 nm, when the reaction time less than 10 min. The wide emission wavelength combine two particle sizes of CdSe, magic and normal, and the magic-CdSe has band-edge and surface-state emission, while normal size only possess band-edge emission. The TEM characterization shows that the two different sizes with diameter of 1.5 nm and 2.7 nm for magic and normal size CdSe QDs can be obtained when the reaction time is 4 min. We can find that the magic size of CdSe is produced when the reaction time is less than 3 min. In the time ranges from 3 to 10 min, two sizes of CdSe QDs are formed, and with QY from 20 to 60 %. Prolong the reaction time to 60 min, only normal size of CdSe QD can be observed due to the Ostwald repining, and its QYs is 8 %. Based on the results we can conclude that the two emission peaks are generated from the coexistence of magic size and normal size CdSe to form the white light QDs, and the QY and emission wavelength of CdSe QDs can be increased with prolonging reaction time. The sample reacts for 2 (QY 30 %), 4 (QY 32 %) and 60 min (QY 8 %) are choosing to mixes with transparent acrylic-based UV curable resin for WLED fabrication. The Commission International d'Eclairage (CIE) chromaticity, color rendering index (CRI), and luminous efficacy for magic, mix, and normal size CdSe are (0.49, 0.44), 81, 1.5 lm/W, (0.35, 0.30), 86, 1.9 lm/W, and (0.39, 0.25), 40, 0.3 lm/W, respectively.

Continuous active surveillance of adverse events following immunisation using SMS technology.

PubMed

Westphal, Darren W; Williams, Stephanie A; Leeb, Alan; Effler, Paul V

2016-06-17

On-going post-licensure surveillance of adverse events following immunisation (AEFI) is critical to detecting and responding to potentially serious adverse events in a timely manner. SmartVax is a vaccine safety monitoring tool that uses automated data extraction from existing practice management software and short message service (SMS) technology to follow-up vaccinees in real-time. We report on childhood vaccine safety surveillance using SmartVax at a medical practice in Perth, Western Australia. Parents of all children under age five years who were vaccinated according to the Australian National Immunisation Schedule between November 2011 and June 2015 were sent an SMS three days post administration to enquire whether the child had experienced a suspected vaccine reaction. Affirmative replies triggered a follow-up SMS requesting details of the reaction(s) via a link to a survey that could be completed using a smartphone or the web. Rates of reported AEFI including fever, headache, fatigue, rash, vomiting, diarrhoea, rigours, seizures, and local reactions were calculated by vaccination time point. Overall, 239 (8.2%; 95% CI 7.2-9.2%) possible vaccine reactions were reported for 2897 vaccination visits over the 44 month time period. The proportion of children experiencing a possible AEFI, mostly local reactions, was significantly greater following administration of diphtheria-tetanus-pertussis-poliomyelitis vaccine at 4 years of age (77/441; 17.5%; 95% CI 13.9-21.0%) compared to the vaccinations given at 2-18 months (p<0.001). Across all time points, local reactions and fatigue were the most frequently reported AEFI. Automated SMS-based reporting can facilitate sustainable, real-time, monitoring of adverse reactions and contribute to early identification of potential vaccine safety issues. Copyright © 2016 Elsevier Ltd. All rights reserved.

Reactivity of fluoroalkanes in reactions of coordinated molecular decomposition

NASA Astrophysics Data System (ADS)

Pokidova, T. S.; Denisov, E. T.

2017-08-01

Experimental results on the coordinated molecular decomposition of RF fluoroalkanes to olefin and HF are analyzed using the model of intersecting parabolas (IPM). The kinetic parameters are calculated to allow estimates of the activation energy ( E) and rate constant ( k) of these reactions, based on enthalpy and IPM algorithms. Parameters E and k are found for the first time for eight RF decomposition reactions. The factors that affect activation energy E of RF decomposition (the enthalpy of the reaction, the electronegativity of the atoms of reaction centers, and the dipole-dipole interaction of polar groups) are determined. The values of E and k for reverse reactions of addition are estimated.

Psychological differences between influence of temperament with the hemishere asymmetry of a brain on size of sensorymotor reactions of male and female cosmonauts

NASA Astrophysics Data System (ADS)

Prisniakova, Lyudmila; Prisniakov, Volodymyr; Volkov, D. S.

The purpose of research was definition and comparison of relative parameters of sensorimotor reactions with a choice depending on a level of lateral asymmetry of hemispheres of a brain at representatives of various types of temperament OF male and female cosmonauts . These parameters were by the bases for verification of theoretical dependence for the latent period of reaction in conditions of weightlessness and overloads. The hypothesis about influence of functional asymmetry on parameters of psychomotor in sensory-motor reactions was laid in a basis of experiment. Techniques of definition of individual characters of the sensori-motor asymmetries were used, and G. Ajzenk's questionnaire EPQ adapted by Prisniakova L. Time of sensorimotor reaction has significant distinctions between representatives of different types of temperament with a various level interchemishere asymmetry OF male and female cosmonauts. With increase in expressiveness of the right hemisphere time of reaction tends to reduction at representatives of all types of temperament, the number of erroneous reactions as a whole increases also a level of achievement tends to reduction. Results of time of sensorimotor reaction correspond with parameter L. Prisniakova which characterizes individual - psychological features. .Earlier the received experimental data of constant time of processing of the information in memory at a period of a sensorimotor reactions of the man and new results for women were used for calculation of these time constants for overloads distinct from terrestrial. These data enable to predict dynamics of behavior of cosmonauts with differing sex in conditions of flight in view of their individual characteristics connected with the hemisphere asymmetry of a brain and with by a various degree of lateralization.

ReactionPredictor: prediction of complex chemical reactions at the mechanistic level using machine learning.

PubMed

Kayala, Matthew A; Baldi, Pierre

2012-10-22

Proposing reasonable mechanisms and predicting the course of chemical reactions is important to the practice of organic chemistry. Approaches to reaction prediction have historically used obfuscating representations and manually encoded patterns or rules. Here we present ReactionPredictor, a machine learning approach to reaction prediction that models elementary, mechanistic reactions as interactions between approximate molecular orbitals (MOs). A training data set of productive reactions known to occur at reasonable rates and yields and verified by inclusion in the literature or textbooks is derived from an existing rule-based system and expanded upon with manual curation from graduate level textbooks. Using this training data set of complex polar, hypervalent, radical, and pericyclic reactions, a two-stage machine learning prediction framework is trained and validated. In the first stage, filtering models trained at the level of individual MOs are used to reduce the space of possible reactions to consider. In the second stage, ranking models over the filtered space of possible reactions are used to order the reactions such that the productive reactions are the top ranked. The resulting model, ReactionPredictor, perfectly ranks polar reactions 78.1% of the time and recovers all productive reactions 95.7% of the time when allowing for small numbers of errors. Pericyclic and radical reactions are perfectly ranked 85.8% and 77.0% of the time, respectively, rising to >93% recovery for both reaction types with a small number of allowed errors. Decisions about which of the polar, pericyclic, or radical reaction type ranking models to use can be made with >99% accuracy. Finally, for multistep reaction pathways, we implement the first mechanistic pathway predictor using constrained tree-search to discover a set of reasonable mechanistic steps from given reactants to given products. Webserver implementations of both the single step and pathway versions of ReactionPredictor are available via the chemoinformatics portal http://cdb.ics.uci.edu/.

Effects of Holding Time, Storage, and the Preservation of Samples on Sample Integrity for the Detection of Fecal Indicator Bacteria by Quantitative Polymerase Chain Reaction (qPCR)-based assays.

EPA Science Inventory

The purpose of this project was to answer questions related to storage of samples to be analyzed by the quantitative polymerase chain reaction (qPCR)-based assays for fecal indicator bacteria. The project was divided into two parts. The first part was to determine if filters th...

DNA dynamics in aqueous solution: opening the double helix

NASA Technical Reports Server (NTRS)

Pohorille, A.; Ross, W. S.; Tinoco, I. Jr; MacElroy, R. D. (Principal Investigator)

1990-01-01

The opening of a DNA base pair is a simple reaction that is a prerequisite for replication, transcription, and other vital biological functions. Understanding the molecular mechanisms of biological reactions is crucial for predicting and, ultimately, controlling them. Realistic computer simulations of the reactions can provide the needed understanding. To model even the simplest reaction in aqueous solution requires hundreds of hours of supercomputing time. We have used molecular dynamics techniques to simulate fraying of the ends of a six base pair double strand of DNA, [TCGCGA]2, where the four bases of DNA are denoted by T (thymine), C (cytosine), G (guanine), and A (adenine), and to estimate the free energy barrier to this process. The calculations, in which the DNA was surrounded by 2,594 water molecules, required 50 hours of CRAY-2 CPU time for every simulated 100 picoseconds. A free energy barrier to fraying, which is mainly characterized by the movement of adenine away from thymine into aqueous environment, was estimated to be 4 kcal/mol. Another fraying pathway, which leads to stacking between terminal adenine and thymine, was also observed. These detailed pictures of the motions and energetics of DNA base pair opening in water are a first step toward understanding how DNA will interact with any molecule.

A Nonequilibrium Rate Formula for Collective Motions of Complex Molecular Systems

NASA Astrophysics Data System (ADS)

Yanao, Tomohiro; Koon, Wang Sang; Marsden, Jerrold E.

2010-09-01

We propose a compact reaction rate formula that accounts for a non-equilibrium distribution of residence times of complex molecules, based on a detailed study of the coarse-grained phase space of a reaction coordinate. We take the structural transition dynamics of a six-atom Morse cluster between two isomers as a prototype of multi-dimensional molecular reactions. Residence time distribution of one of the isomers shows an exponential decay, while that of the other isomer deviates largely from the exponential form and has multiple peaks. Our rate formula explains such equilibrium and non-equilibrium distributions of residence times in terms of the rates of diffusions of energy and the phase of the oscillations of the reaction coordinate. Rapid diffusions of energy and the phase generally give rise to the exponential decay of residence time distribution, while slow diffusions give rise to a non-exponential decay with multiple peaks. We finally make a conjecture about a general relationship between the rates of the diffusions and the symmetry of molecular mass distributions.

Low-temperature rapid synthesis and superconductivity of Fe-based oxypnictide superconductors.

PubMed

Fang, Ai-Hua; Huang, Fu-Qiang; Xie, Xiao-Ming; Jiang, Mian-Heng

2010-03-17

Fe-based oxypnictide superconductors were successfully synthesized at lower reaction temperatures and with shorter reaction times made possible by starting with less stable compounds, which provide a larger driving force for reactions. Using ball-milled powders of intermediate compounds, phase-pure superconductors with T(c) above 50 K were synthesized at 1173 K in 20 min. This method is particularly advantageous for retaining F, a volatile dopant that enhances superconductivity. Bulk superconductivity and high upper critical fields up to 392 T in Sm(0.85)Nd(0.15)FeAsO(0.85)F(0.15) were demonstrated.

A more robust model of the biodiesel reaction, allowing identification of process conditions for significantly enhanced rate and water tolerance.

PubMed

Eze, Valentine C; Phan, Anh N; Harvey, Adam P

2014-03-01

A more robust kinetic model of base-catalysed transesterification than the conventional reaction scheme has been developed. All the relevant reactions in the base-catalysed transesterification of rapeseed oil (RSO) to fatty acid methyl ester (FAME) were investigated experimentally, and validated numerically in a model implemented using MATLAB. It was found that including the saponification of RSO and FAME side reactions and hydroxide-methoxide equilibrium data explained various effects that are not captured by simpler conventional models. Both the experiment and modelling showed that the "biodiesel reaction" can reach the desired level of conversion (>95%) in less than 2min. Given the right set of conditions, the transesterification can reach over 95% conversion, before the saponification losses become significant. This means that the reaction must be performed in a reactor exhibiting good mixing and good control of residence time, and the reaction mixture must be quenched rapidly as it leaves the reactor. Copyright © 2014 Elsevier Ltd. All rights reserved.

Gaseous species as reaction tracers in the solvothermal synthesis of the zinc oxide terephthalate MOF-5.

PubMed

Hausdorf, Steffen; Baitalow, Felix; Seidel, Jürgen; Mertens, Florian O R L

2007-05-24

Gaseous species emitted during the zinc oxide/zinc hydroxide 1,4-benzenedicarboxylate metal organic framework synthesis (MOF-5, MOF-69c) have been used to investigate the reaction scheme that leads to the framework creation. Changes of the gas-phase composition over time indicate that the decomposition of the solvent diethylformamide occurs at least via two competing reaction pathways that can be linked to the reaction's overall water and pH management. From isotope exchange experiments, we deduce that one of the decomposition pathways leads to the removal of water from the reaction mixture, which sets the conditions when the synthesis of an oxide-based (MOF-5) instead of an hydroxide-based MOF (MOF-69c) occurs. A quantitative account of most reactants and byproducts before and after the MOF-5/MOF-69c synthesis is presented. From the investigation of the reaction intermediates and byproducts, we derive a proposal of a basic reaction scheme for the standard synthesis zinc oxide carboxylate MOFs.

A Short Interspersed Nuclear Element (SINE)-Based Real-Time PCR Approach to Detect and Quantify Porcine Component in Meat Products.

PubMed

Zhang, Chi; Fang, Xin; Qiu, Haopu; Li, Ning

2015-01-01

Real-time PCR amplification of mitochondria gene could not be used for DNA quantification, and that of single copy DNA did not allow an ideal sensitivity. Moreover, cross-reactions among similar species were commonly observed in the published methods amplifying repetitive sequence, which hindered their further application. The purpose of this study was to establish a short interspersed nuclear element (SINE)-based real-time PCR approach having high specificity for species detection that could be used in DNA quantification. After massive screening of candidate Sus scrofa SINEs, one optimal combination of primers and probe was selected, which had no cross-reaction with other common meat species. LOD of the method was 44 fg DNA/reaction. Further, quantification tests showed this approach was practical in DNA estimation without tissue variance. Thus, this study provided a new tool for qualitative detection of porcine component, which could be promising in the QC of meat products.

Stress reaction process-based hierarchical recognition algorithm for continuous intrusion events in optical fiber prewarning system

NASA Astrophysics Data System (ADS)

Qu, Hongquan; Yuan, Shijiao; Wang, Yanping; Yang, Dan

2018-04-01

To improve the recognition performance of optical fiber prewarning system (OFPS), this study proposed a hierarchical recognition algorithm (HRA). Compared with traditional methods, which employ only a complex algorithm that includes multiple extracted features and complex classifiers to increase the recognition rate with a considerable decrease in recognition speed, HRA takes advantage of the continuity of intrusion events, thereby creating a staged recognition flow inspired by stress reaction. HRA is expected to achieve high-level recognition accuracy with less time consumption. First, this work analyzed the continuity of intrusion events and then presented the algorithm based on the mechanism of stress reaction. Finally, it verified the time consumption through theoretical analysis and experiments, and the recognition accuracy was obtained through experiments. Experiment results show that the processing speed of HRA is 3.3 times faster than that of a traditional complicated algorithm and has a similar recognition rate of 98%. The study is of great significance to fast intrusion event recognition in OFPS.

A recombinase polymerase amplification-based assay for rapid detection of African swine fever virus.

PubMed

Wang, Jianchang; Wang, Jinfeng; Geng, Yunyun; Yuan, Wanzhe

2017-10-01

A recombinase polymerase amplification (RPA)-based method was developed for rapid and specific detection of African swine fever virus (ASFV), the etiologic agent of African swine fever, a devastating disease of swine. Primers and the exo probe targeting the conserved region of the P72 gene of ASFV were designed and the reaction was run on the Genie III scanner device. Using recombinant plasmid DNA containing the P72 gene as template, we showed that the amplified product could be detected in less than 10 min and that the detection limit was 10 2 copies DNA/reaction [same detection limit as real-time polymerase chain reaction (PCR)]. The RPA assay did not cross-detect CSFV, PCV-2, PRV, PRRSV, or FMDV, common viruses seen in pigs. Tests of recombinant plasmid-spiked serum samples revealed that RPA and real-time PCR had the same diagnostic rate. The RPA assay, which is simple, cost-effective, and fast, is a promising alternative to real-time PCR for ASFV detection.

A recombinase polymerase amplification-based assay for rapid detection of African swine fever virus

PubMed Central

Wang, Jianchang; Wang, Jinfeng; Geng, Yunyun; Yuan, Wanzhe

2017-01-01

A recombinase polymerase amplification (RPA)-based method was developed for rapid and specific detection of African swine fever virus (ASFV), the etiologic agent of African swine fever, a devastating disease of swine. Primers and the exo probe targeting the conserved region of the P72 gene of ASFV were designed and the reaction was run on the Genie III scanner device. Using recombinant plasmid DNA containing the P72 gene as template, we showed that the amplified product could be detected in less than 10 min and that the detection limit was 102 copies DNA/reaction [same detection limit as real-time polymerase chain reaction (PCR)]. The RPA assay did not cross-detect CSFV, PCV-2, PRV, PRRSV, or FMDV, common viruses seen in pigs. Tests of recombinant plasmid-spiked serum samples revealed that RPA and real-time PCR had the same diagnostic rate. The RPA assay, which is simple, cost-effective, and fast, is a promising alternative to real-time PCR for ASFV detection. PMID:29081590

Effect of Maillard reaction products on the physical and antimicrobial properties of edible films based on ε-polylysine and chitosan.

PubMed

Wang, Yingying; Liu, Fuguo; Liang, Chunxuan; Yuan, Fang; Gao, Yanxiang

2014-11-01

Edible films based on Maillard reaction products (MRPs) of ε-polylysine and chitosan, without the use of any plasticiser, were prepared by solution casting. The effect of Maillard reaction parameters (reaction time and the ratio of polylysine/chitosan) of ε-polylysine and chitosan on the structure, moisture content, water solubility, total colour difference and mechanical properties of edible films formed by MRPs were systematically evaluated. Scanning electron microscopy confirmed that edible films prepared by the MRPs of ε-polylysine and chitosan through the Maillard reaction exhibited a more compact and dense structure than those from the mixture of biopolymers without the presence of MRPs. The tensile strength and % elongation values of films from the mixture were decreased significantly with the rise of ε-polylysine (P < 0.05). The moisture content of the films was not significantly affected by Maillard reaction, whereas water solubility was decreased and total colour difference was increased significantly (P < 0.05) with the extension of Maillard reaction time. In addition, antimicrobial activity of chitosan films against E. coli and S. aureus. could be achieved by incorporating ε-polylysine into chitosan. These films can ensure food quality and safety, especially for coating highly perishable foods, such as meat products. © 2014 Society of Chemical Industry. © 2014 Society of Chemical Industry.

Enzymatic synthesis of chiral amino‐alcohols by coupling transketolase and transaminase‐catalyzed reactions in a cascading continuous‐flow microreactor system

PubMed Central

Gruber, Pia; Carvalho, Filipe; Marques, Marco P. C.; O'Sullivan, Brian; Subrizi, Fabiana; Dobrijevic, Dragana; Ward, John; Hailes, Helen C.; Fernandes, Pedro; Wohlgemuth, Roland; Baganz, Frank

2017-01-01

Abstract Rapid biocatalytic process development and intensification continues to be challenging with currently available methods. Chiral amino‐alcohols are of particular interest as they represent key industrial synthons for the production of complex molecules and optically pure pharmaceuticals. (2S,3R)‐2‐amino‐1,3,4‐butanetriol (ABT), a building block for the synthesis of protease inhibitors and detoxifying agents, can be synthesized from simple, non‐chiral starting materials, by coupling a transketolase‐ and a transaminase‐catalyzed reaction. However, until today, full conversion has not been shown and, typically, long reaction times are reported, making process modifications and improvement challenging. In this contribution, we present a novel microreactor‐based approach based on free enzymes, and we report for the first time full conversion of ABT in a coupled enzyme cascade for both batch and continuous‐flow systems. Using the compartmentalization of the reactions afforded by the microreactor cascade, we overcame inhibitory effects, increased the activity per unit volume, and optimized individual reaction conditions. The transketolase‐catalyzed reaction was completed in under 10 min with a volumetric activity of 3.25 U ml−1. Following optimization of the transaminase‐catalyzed reaction, a volumetric activity of 10.8 U ml−1 was attained which led to full conversion of the coupled reaction in 2 hr. The presented approach illustrates how continuous‐flow microreactors can be applied for the design and optimization of biocatalytic processes. PMID:28986983

Reaction Time and Established Risk Factors for Total and Cardiovascular Disease Mortality: Comparison of Effect Estimates in the Follow-Up of a Large, UK-Wide, General-Population Based Survey

ERIC Educational Resources Information Center

Roberts, Beverly A.; Der, Geoff; Deary, Ian J.; Batty, G. David

2009-01-01

Higher cognitive function is associated with faster choice reaction time (CRT), and both are associated with a reduced risk of mortality from all-causes and cardiovascular disease (CVD). However, comparison of the predictive capacity of CRT, an emerging risk factor, with that for established "classic" risk factors for mortality, such as…

Effect of Substrate Concentration and Reaction Time of Aquilaria subintegra Leaves Extract on Inhibition of Pancreatic Lipase

NASA Astrophysics Data System (ADS)

Zainal, S.; Musa, M.; Idris, J.; Hamid, K. H. Ku

2018-05-01

The purpose of this research are to recovery of pancreatic lipase inhibitor and to study the effect of using different concentration of substrate and reaction time on pancreatic lipase inhibitor. In this research, Aquilaria subintegra mature and fresh leaves was used as a sample. The research was conducted by using hydro-distillation with different concentrations, which are 100 µM, 200 µM and 300 µM and reaction times from 20, 40 and 60 minutes were studied. Based on the results obtained for the samples of phenol, flavonoid, gallic acid and quercetin were 49.30 µg/ml, 314.33 µg/ml, 12.94 µg/ml, and 5.15 µg/ml, respectively.

A DAG Scheduling Scheme on Heterogeneous Computing Systems Using Tuple-Based Chemical Reaction Optimization

PubMed Central

Jiang, Yuyi; Shao, Zhiqing; Guo, Yi

2014-01-01

A complex computing problem can be solved efficiently on a system with multiple computing nodes by dividing its implementation code into several parallel processing modules or tasks that can be formulated as directed acyclic graph (DAG) problems. The DAG jobs may be mapped to and scheduled on the computing nodes to minimize the total execution time. Searching an optimal DAG scheduling solution is considered to be NP-complete. This paper proposed a tuple molecular structure-based chemical reaction optimization (TMSCRO) method for DAG scheduling on heterogeneous computing systems, based on a very recently proposed metaheuristic method, chemical reaction optimization (CRO). Comparing with other CRO-based algorithms for DAG scheduling, the design of tuple reaction molecular structure and four elementary reaction operators of TMSCRO is more reasonable. TMSCRO also applies the concept of constrained critical paths (CCPs), constrained-critical-path directed acyclic graph (CCPDAG) and super molecule for accelerating convergence. In this paper, we have also conducted simulation experiments to verify the effectiveness and efficiency of TMSCRO upon a large set of randomly generated graphs and the graphs for real world problems. PMID:25143977

A DAG scheduling scheme on heterogeneous computing systems using tuple-based chemical reaction optimization.

PubMed

Jiang, Yuyi; Shao, Zhiqing; Guo, Yi

2014-01-01

A complex computing problem can be solved efficiently on a system with multiple computing nodes by dividing its implementation code into several parallel processing modules or tasks that can be formulated as directed acyclic graph (DAG) problems. The DAG jobs may be mapped to and scheduled on the computing nodes to minimize the total execution time. Searching an optimal DAG scheduling solution is considered to be NP-complete. This paper proposed a tuple molecular structure-based chemical reaction optimization (TMSCRO) method for DAG scheduling on heterogeneous computing systems, based on a very recently proposed metaheuristic method, chemical reaction optimization (CRO). Comparing with other CRO-based algorithms for DAG scheduling, the design of tuple reaction molecular structure and four elementary reaction operators of TMSCRO is more reasonable. TMSCRO also applies the concept of constrained critical paths (CCPs), constrained-critical-path directed acyclic graph (CCPDAG) and super molecule for accelerating convergence. In this paper, we have also conducted simulation experiments to verify the effectiveness and efficiency of TMSCRO upon a large set of randomly generated graphs and the graphs for real world problems.

μ-PADs for detection of chemical warfare agents.

PubMed

Pardasani, Deepak; Tak, Vijay; Purohit, Ajay K; Dubey, D K

2012-12-07

Conventional methods of detection of chemical warfare agents (CWAs) based on chromogenic reactions are time and solvent intensive. The development of cost, time and solvent effective microfluidic paper based analytical devices (μ-PADs) for the detection of nerve and vesicant agents is described. The detection of analytes was based upon their reactions with rhodamine hydroxamate and para-nitrobenzyl pyridine, producing red and blue colours respectively. Reactions were optimized on the μ-PADs to produce the limits of detection (LODs) as low as 100 μM for sulfur mustard in aqueous samples. Results were quantified with the help of a simple desktop scanner and Photoshop software. Sarin achieved a linear response in the two concentration ranges of 20-100 mM and 100-500 mM, whereas the response of sulfur mustard was found to be linear in the concentration range of 10-75 mM. Results were precise enough to establish the μ-PADs as a valuable tool for security personnel fighting against chemical terrorism.

High utilization ratio of metal organic sources for MOCVD-derived GdYBCO films based on a narrow channel reaction chamber

NASA Astrophysics Data System (ADS)

Zhao, Ruipeng; Liu, Qing; Xia, Yudong; Tang, Hao; Lu, Yuming; Cai, Chuanbing; Tao, Bowan; Li, Yanrong

2018-01-01

A narrow channel reaction chamber is designed in our home-made MOCVD system and applied to deposit GdYBCO films on the template of LaMnO3/epitaxial MgO/IBAD-MgO/solution deposition planarization-Y2O3-buffered Hastelloy tapes. In the reaction chamber, metal organic sources are transferred from the inlet to the outlet along the direction of the tape movement. Thus, compared to the vertical injection way of metal organic sources, the residence time of metal organic sources on the surface of substrates would be extended through adopting the novel reaction chamber. Therefore, the utilization of metal organic sources, which is calculated according to the measured results of experiments, can reach 31%. Additionally, the utilization ratio of metal organic sources based on the novel reaction chamber is basically two times as much as that of the commonly used vertical injection slit shower. What is more, through adjusting the process, the critical current density of 300 nm thick GdYBCO film prepared the reel-to-reel way has reached 3.2 MA cm-2 (77 K, 0 T).

PID Controller Settings Based on a Transient Response Experiment

ERIC Educational Resources Information Center

Silva, Carlos M.; Lito, Patricia F.; Neves, Patricia S.; Da Silva, Francisco A.

2008-01-01

An experimental work on controller tuning for chemical engineering undergraduate students is proposed using a small heat exchange unit. Based upon process reaction curves in open-loop configuration, system gain and time constant are determined for first order model with time delay with excellent accuracy. Afterwards students calculate PID…

Stochastic flux analysis of chemical reaction networks

PubMed Central

2013-01-01

Background Chemical reaction networks provide an abstraction scheme for a broad range of models in biology and ecology. The two common means for simulating these networks are the deterministic and the stochastic approaches. The traditional deterministic approach, based on differential equations, enjoys a rich set of analysis techniques, including a treatment of reaction fluxes. However, the discrete stochastic simulations, which provide advantages in some cases, lack a quantitative treatment of network fluxes. Results We describe a method for flux analysis of chemical reaction networks, where flux is given by the flow of species between reactions in stochastic simulations of the network. Extending discrete event simulation algorithms, our method constructs several data structures, and thereby reveals a variety of statistics about resource creation and consumption during the simulation. We use these structures to quantify the causal interdependence and relative importance of the reactions at arbitrary time intervals with respect to the network fluxes. This allows us to construct reduced networks that have the same flux-behavior, and compare these networks, also with respect to their time series. We demonstrate our approach on an extended example based on a published ODE model of the same network, that is, Rho GTP-binding proteins, and on other models from biology and ecology. Conclusions We provide a fully stochastic treatment of flux analysis. As in deterministic analysis, our method delivers the network behavior in terms of species transformations. Moreover, our stochastic analysis can be applied, not only at steady state, but at arbitrary time intervals, and used to identify the flow of specific species between specific reactions. Our cases study of Rho GTP-binding proteins reveals the role played by the cyclic reverse fluxes in tuning the behavior of this network. PMID:24314153

Robust, Chiral, and Porous BINAP-Based Metal–Organic Frameworks for Highly Enantioselective Cyclization Reactions

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

Sawano, Takahiro; Thacker, Nathan C.; Lin, Zekai

2016-05-06

We report here the design of BINAP-based metal–organic frameworks and their postsynthetic metalation with Rh complexes to afford highly active and enantioselective single-site solid catalysts for the asymmetric cyclization reactions of 1,6-enynes. Robust, chiral, and porous Zr-MOFs of UiO topology, BINAP-MOF (I) or BINAP-dMOF (II), were prepared using purely BINAP-derived dicarboxylate linkers or by mixing BINAP-derived linkers with unfunctionalized dicarboxylate linkers, respectively. Upon metalation with Rh(nbd)2BF4 and [Rh(nbd)Cl]2/AgSbF6, the MOF precatalysts I·Rh(BF4) and I·Rh(SbF6) efficiently catalyzed highly enantioselective (up to 99% ee) reductive cyclization and Alder-ene cycloisomerization of 1,6-enynes, respectively. I·Rh catalysts afforded cyclization products at comparable enantiomeric excesses (ee’s)more » and 4–7 times higher catalytic activity than the homogeneous controls, likely a result of catalytic site isolation in the MOF which prevents bimolecular catalyst deactivation pathways. However, I·Rh is inactive in the more sterically encumbered Pauson–Khand reactions between 1,6-enynes and carbon monoxide. In contrast, with a more open structure, Rh-functionalized BINAP-dMOF, II·Rh, effectively catalyzed Pauson–Khand cyclization reactions between 1,6-enynes and carbon monoxide at 10 times higher activity than the homogeneous control. II·Rh was readily recovered and used three times in Pauson–Khand cyclization reactions without deterioration of yields or ee’s. Our work has expanded the scope of MOF-catalyzed asymmetric reactions and showed that the mixed linker strategy can effectively enlarge the open space around the catalytic active site to accommodate highly sterically demanding polycyclic metallocycle transition states/intermediates in asymmetric intramolecular cyclization reactions.« less

Stochastic flux analysis of chemical reaction networks.

PubMed

Kahramanoğulları, Ozan; Lynch, James F

2013-12-07

Chemical reaction networks provide an abstraction scheme for a broad range of models in biology and ecology. The two common means for simulating these networks are the deterministic and the stochastic approaches. The traditional deterministic approach, based on differential equations, enjoys a rich set of analysis techniques, including a treatment of reaction fluxes. However, the discrete stochastic simulations, which provide advantages in some cases, lack a quantitative treatment of network fluxes. We describe a method for flux analysis of chemical reaction networks, where flux is given by the flow of species between reactions in stochastic simulations of the network. Extending discrete event simulation algorithms, our method constructs several data structures, and thereby reveals a variety of statistics about resource creation and consumption during the simulation. We use these structures to quantify the causal interdependence and relative importance of the reactions at arbitrary time intervals with respect to the network fluxes. This allows us to construct reduced networks that have the same flux-behavior, and compare these networks, also with respect to their time series. We demonstrate our approach on an extended example based on a published ODE model of the same network, that is, Rho GTP-binding proteins, and on other models from biology and ecology. We provide a fully stochastic treatment of flux analysis. As in deterministic analysis, our method delivers the network behavior in terms of species transformations. Moreover, our stochastic analysis can be applied, not only at steady state, but at arbitrary time intervals, and used to identify the flow of specific species between specific reactions. Our cases study of Rho GTP-binding proteins reveals the role played by the cyclic reverse fluxes in tuning the behavior of this network.

In situ loading of well-dispersed silver nanoparticles on nanocrystalline magnesium oxide for real-time monitoring of catalytic reactions by surface enhanced Raman spectroscopy.

PubMed

Zhang, Kaige; Li, Gongke; Hu, Yuling

2015-10-28

The surface-enhanced Raman spectroscopy (SERS) technique is of great importance for insight into the transient reaction intermediates and mechanistic pathways involved in heterogeneously catalyzed chemical reactions under actual reaction conditions, especially in water. Herein, we demonstrate a facile method for in situ synthesis of nanocrystalline magnesium oxide-Ag(0) (nano MgO-Ag(0)) hybrid nanomaterials with dispersed Ag nanoparticles (Ag NPs) on the surface of nanocrystalline magnesium oxide (nano MgO) via Sn(2+) linkage and reduction. As a benefit from the synergy effect of nano MgO and Ag NPs, the nano MgO-Ag(0) exhibited both excellent SERS and catalytic activities for the reduction of 4-nitrothiophenol in the presence of NaBH4. The nano MgO-Ag(0) was used for real-time monitoring of the catalytic reaction process of 4-nitrothiophenol to 4-aminothiophenol in an aqueous medium by observing the SERS signals of the reactant, intermediate and final products. The intrinsic reaction kinetics and reaction mechanism of this reaction were also investigated. This SERS-based synergy technique provides a novel approach for quantitative in situ monitoring of catalytic chemical reaction processes.

Colloidal nanomaterial-based immunoassay.

PubMed

Teste, Bruno; Descroix, Stephanie

2012-06-01

Nanomaterials have been widely developed for their use in nanomedicine, especially for immunoassay-based diagnosis. In this review we focus on the use of nanomaterials as a nanoplatform for colloidal immunoassays. While conventional heterogeneous immunoassays suffer from mass transfer limitations and consequently long assay time, colloidal immunosupports allow target capture in the entire volume, thus speeding up reaction kinetics and shortening assay time. Owing to their wide range of chemical and physical properties, nanomaterials are an interesting candidate for immunoassay development. The most popular colloidal nanomaterials for colloidal immunoassays will be discussed, as well as their influence on immune reactions. Recent advances in nanomaterial applications for different formats of immunoassays will be reported, such as nanomaterial-based indirect immunoassays, optical-based agglutination immunoassays, resonance energy transfer-based immunoassays and magnetic relaxation-based immunoassays. Finally, the future of using nanomaterials for homogeneous immunoassays dedicated to clinical diagnosis will be discussed.

Trial-Level Regressor Modulation for Functional Magnetic Resonance Imaging Designs Requiring Strict Periodicity of Stimulus Presentations: Illustrated Using a Go/No-Go Task.

PubMed

Motes, Michael A; Rao, Neena K; Shokri-Kojori, Ehsan; Chiang, Hsueh-Sheng; Kraut, Michael A; Hart, John

2017-01-01

Computer-based assessment of many cognitive processes (eg, anticipatory and response readiness processes) requires the use of invariant stimulus display times (SDT) and intertrial intervals (ITI). Although designs with invariant SDTs and ITIs have been used in functional magnetic resonance imaging (fMRI) research, such designs are problematic for fMRI studies because of collinearity issues. This study examined regressor modulation with trial-level reaction times (RT) as a method for improving signal detection in a go / no-go task with invariant SDTs and ITIs. The effects of modulating the go regressor were evaluated with respect to the detection of BOLD signal-change for the no-go condition. BOLD signal-change to no-go stimuli was examined when the go regressor was based on a (a) canonical hemodynamic response function (HRF), (b) RT-based amplitude-modulated (AM) HRF, and (c) RT-based amplitude and duration modulated (A&DM) HRF. Reaction time-based modulation reduced the collinearity between the go and no-go regressors, with A&DM producing the greatest reductions in correlations between the regressors, and greater reductions in the correlations between regressors were associated with longer mean RTs and greater RT variability. Reaction time-based modulation increased statistical power for detecting group-level no-go BOLD signal-change across a broad set of brain regions. The findings show the efficacy of using regressor modulation to increase power in detecting BOLD signal-change in fMRI studies in which circumstances dictate the use of temporally invariant stimulus presentations.

Numerical simulation of two-dimensional flow over a heated carbon surface with coupled heterogeneous and homogeneous reactions

NASA Astrophysics Data System (ADS)

Johnson, Ryan Federick; Chelliah, Harsha Kumar

2017-01-01

For a range of flow and chemical timescales, numerical simulations of two-dimensional laminar flow over a reacting carbon surface were performed to understand further the complex coupling between heterogeneous and homogeneous reactions. An open-source computational package (OpenFOAM®) was used with previously developed lumped heterogeneous reaction models for carbon surfaces and a detailed homogeneous reaction model for CO oxidation. The influence of finite-rate chemical kinetics was explored by varying the surface temperatures from 1800 to 2600 K, while flow residence time effects were explored by varying the free-stream velocity up to 50 m/s. The reacting boundary layer structure dependence on the residence time was analysed by extracting the ratio of chemical source and species diffusion terms. The important contributions of radical species reactions on overall carbon removal rate, which is often neglected in multi-dimensional simulations, are highlighted. The results provide a framework for future development and validation of lumped heterogeneous reaction models based on multi-dimensional reacting flow configurations.

Sexing chick mRNA: A protocol based on quantitative real-time polymerase chain reaction.

PubMed

Wan, Z; Lu, Y; Rui, L; Yu, X; Li, Z

2017-03-01

The accurate identification of sex in birds is important for research on avian sex determination and differentiation. Polymerase chain reaction (PCR)-based methods have been widely applied for the molecular sexing of birds. However, these methods have used genomic DNA. Here, we present the first sexing protocol for chick mRNA based on real-time quantitative PCR. We demonstrate that this method can accurately determine sex using mRNA from chick gonads and other tissues, such as heart, liver, spleen, lung, and muscle. The strategy of this protocol also may be suitable for other species in which sex is determined by the inheritance of sex chromosomes (ZZ male and ZW female). © 2016 Poultry Science Association Inc.

Learning to predict chemical reactions.

PubMed

Kayala, Matthew A; Azencott, Chloé-Agathe; Chen, Jonathan H; Baldi, Pierre

2011-09-26

Being able to predict the course of arbitrary chemical reactions is essential to the theory and applications of organic chemistry. Approaches to the reaction prediction problems can be organized around three poles corresponding to: (1) physical laws; (2) rule-based expert systems; and (3) inductive machine learning. Previous approaches at these poles, respectively, are not high throughput, are not generalizable or scalable, and lack sufficient data and structure to be implemented. We propose a new approach to reaction prediction utilizing elements from each pole. Using a physically inspired conceptualization, we describe single mechanistic reactions as interactions between coarse approximations of molecular orbitals (MOs) and use topological and physicochemical attributes as descriptors. Using an existing rule-based system (Reaction Explorer), we derive a restricted chemistry data set consisting of 1630 full multistep reactions with 2358 distinct starting materials and intermediates, associated with 2989 productive mechanistic steps and 6.14 million unproductive mechanistic steps. And from machine learning, we pose identifying productive mechanistic steps as a statistical ranking, information retrieval problem: given a set of reactants and a description of conditions, learn a ranking model over potential filled-to-unfilled MO interactions such that the top-ranked mechanistic steps yield the major products. The machine learning implementation follows a two-stage approach, in which we first train atom level reactivity filters to prune 94.00% of nonproductive reactions with a 0.01% error rate. Then, we train an ensemble of ranking models on pairs of interacting MOs to learn a relative productivity function over mechanistic steps in a given system. Without the use of explicit transformation patterns, the ensemble perfectly ranks the productive mechanism at the top 89.05% of the time, rising to 99.86% of the time when the top four are considered. Furthermore, the system is generalizable, making reasonable predictions over reactants and conditions which the rule-based expert does not handle. A web interface to the machine learning based mechanistic reaction predictor is accessible through our chemoinformatics portal ( http://cdb.ics.uci.edu) under the Toolkits section.

Learning to Predict Chemical Reactions

PubMed Central

Kayala, Matthew A.; Azencott, Chloé-Agathe; Chen, Jonathan H.

2011-01-01

Being able to predict the course of arbitrary chemical reactions is essential to the theory and applications of organic chemistry. Approaches to the reaction prediction problems can be organized around three poles corresponding to: (1) physical laws; (2) rule-based expert systems; and (3) inductive machine learning. Previous approaches at these poles respectively are not high-throughput, are not generalizable or scalable, or lack sufficient data and structure to be implemented. We propose a new approach to reaction prediction utilizing elements from each pole. Using a physically inspired conceptualization, we describe single mechanistic reactions as interactions between coarse approximations of molecular orbitals (MOs) and use topological and physicochemical attributes as descriptors. Using an existing rule-based system (Reaction Explorer), we derive a restricted chemistry dataset consisting of 1630 full multi-step reactions with 2358 distinct starting materials and intermediates, associated with 2989 productive mechanistic steps and 6.14 million unproductive mechanistic steps. And from machine learning, we pose identifying productive mechanistic steps as a statistical ranking, information retrieval, problem: given a set of reactants and a description of conditions, learn a ranking model over potential filled-to-unfilled MO interactions such that the top ranked mechanistic steps yield the major products. The machine learning implementation follows a two-stage approach, in which we first train atom level reactivity filters to prune 94.00% of non-productive reactions with a 0.01% error rate. Then, we train an ensemble of ranking models on pairs of interacting MOs to learn a relative productivity function over mechanistic steps in a given system. Without the use of explicit transformation patterns, the ensemble perfectly ranks the productive mechanism at the top 89.05% of the time, rising to 99.86% of the time when the top four are considered. Furthermore, the system is generalizable, making reasonable predictions over reactants and conditions which the rule-based expert does not handle. A web interface to the machine learning based mechanistic reaction predictor is accessible through our chemoinformatics portal (http://cdb.ics.uci.edu) under the Toolkits section. PMID:21819139

Mechanism-Based Condition Screening for Sustainable Catalysis in Single-Electron Steps by Cyclic Voltammetry.

PubMed

Liedtke, Theresa; Spannring, Peter; Riccardi, Ludovico; Gansäuer, Andreas

2018-04-23

A cyclic-voltammetry-based screening method for Cp 2 TiX-catalyzed reactions is introduced. Our mechanism-based approach enables the study of the influence of various additives on the electrochemically generated active catalyst Cp 2 TiX, which is in equilibrium with catalytically inactive [Cp 2 TiX 2 ] - . Thioureas and ureas are most efficient in the generation of Cp 2 TiX in THF. Knowing the precise position of the equilibrium between Cp 2 TiX and [Cp 2 TiX 2 ] - allowed us to identify reaction conditions for the bulk electrolysis of Cp 2 TiX 2 complexes and for Cp 2 TiX-catayzed radical arylations without having to carry out the reactions. Our time- and resource-efficient approach is of general interest for the design of catalytic reactions that proceed in single-electron steps. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spin-labelled diketopiperazines and peptide-peptoid chimera by Ugi-multi-component-reactions.

PubMed

Sultani, Haider N; Haeri, Haleh H; Hinderberger, Dariush; Westermann, Bernhard

2016-12-28

For the first time, spin-labelled coumpounds have been obtained by isonitrile-based multi component reactions (IMCRs). The typical IMCR Ugi-protocols offer a simple experimental setup allowing structural variety by which labelled diketopiperazines (DKPs) and peptide-peptoid chimera have been synthesized. The reaction keeps the paramagnetic spin label intact and offers a simple and versatile route to a large variety of new and chemically diverse spin labels.

Oil-encapsulated nanodroplet array for bio-molecular detection.

PubMed

Qiao, Wen; Zhang, Tiantian; Yen, Tony; Ku, Ti-Hsuan; Song, Junlan; Lian, Ian; Lo, Yu-Hwa

2014-09-01

Detection of low abundance biomolecules is challenging for biosensors that rely on surface chemical reactions. For surface reaction based biosensors, it require to take hours or even days for biomolecules of diffusivities in the order of 10(-10-11) m2/s to reach the surface of the sensors by Brownian motion. In addition, often times the repelling Coulomb interactions between the molecules and the probes further defer the binding process, leading to undesirably long detection time for applications such as point-of-care in vitro diagnosis. In this work, we designed an oil encapsulated nanodroplet array microchip utilizing evaporation for pre-concentration of the targets to greatly shorten the reaction time and enhance the detection sensitivity. The evaporation process of the droplets is facilitated by the superhydrophilic surface and resulting nanodroplets are encapsulated by oil drops to form stable reaction chamber. Using this method, desirable droplet volumes, concentrations of target molecules, and reaction conditions (salt concentrations, reaction temperature, etc.) in favour of fast and sensitive detection are obtained. A linear response over 2 orders of magnitude in target concentration was achieved at 10 fM for protein targets and 100 fM for miRNA mimic oligonucleotides.

Analysis of reaction products formed in the gas phase reaction of E,E-2,4-hexadienal with atmospheric oxidants: Reaction mechanisms and atmospheric implications

NASA Astrophysics Data System (ADS)

Colmenar, I.; Martin, P.; Cabañas, B.; Salgado, S.; Martinez, E.

2018-03-01

An analysis of reaction products for the reaction of E,E-2,4-hexadienal with chlorine atoms (Cl) and OH and NO3 radicals has been carried out at the first time with the aim of obtaining a better understanding of the tropospheric reactivity of α,β-unsaturated carbonyl compounds. Fourier Transform Infrared (FTIR) spectroscopy and Gas Chromatography-Mass Spectrometry with a Time of Flight detector (GC-TOFMS) were used to carry out the qualitative and/or quantitative analyses. Reaction products in gas and particulate phase were observed from the reactions of E,E-2,4- hexadienal with all oxidants. E/Z-Butenedial and maleic anhydride were the main products identified in gas phase. E-butenedial calculated molar yield ranging from 4 to 10%. A significant amount of multifunctional compounds (chloro and hydroxy carbonyls) was identified. These compounds could be formed in particulate phase explaining the ∼90% of unaccounted carbon in gas phase. The reaction with Cl atoms in the presence of NOx with a long reaction time gave Peroxy Acetyl Nitrate (PAN) as an additional product, which is known for being an important specie in the generation of the photochemical smog. Nitrated compounds were the major organic products from the reaction with the NO3 radical. Based on the identified products, the reaction mechanisms have been proposed. In these mechanisms a double bond addition of the atmospheric oxidant at C4/C5 of E,E-2,4-hexadienal is the first step for tropospheric degradation.

Development of polymerase chain reaction-based diagnostic tests for detection of Malsoor virus & adenovirus isolated from Rousettus species of bats in Maharashtra, India.

PubMed

Shete, Anita M; Yadav, Pragya; Kumar, Vimal; Nikam, Tushar; Mehershahi, Kurosh; Kokate, Prasad; Patil, Deepak; Mourya, Devendra T

2017-01-01

Bats are recognized as important reservoirs for emerging infectious disease and some unknown viral diseases. Two novel viruses, Malsoor virus (family Bunyaviridae, genus, Phlebovirus) and a novel adenovirus (AdV) (family, Adenoviridae genus, Mastadenovirus), were identified from Rousettus bats in the Maharashtra State of India. This study was done to develop and optimize real time reverse transcription - polymerase chain reaction (RT-PCR) assays for Malsoor virus and real time and nested PCR for adenovirus from Rousettus bats. For rapid and accurate screening of Malsoor virus and adenovirus a nested polymerase chain reaction and TaqMan-based real-time PCR were developed. Highly conserved region of nucleoprotein gene of phleboviruses and polymerase gene sequence from the Indian bat AdV isolate polyprotein gene were selected respectively for diagnostic assay development of Malsoor virus and AdV. Sensitivity and specificity of assays were calculated and optimized assays were used to screen bat samples. Molecular diagnostic assays were developed for screening of Malsoor virus and AdV and those were found to be specific. Based on the experiments performed with different parameters, nested PCR was found to be more sensitive than real-time PCR; however, for rapid screening, real-time PCR can be used and further nested PCR can be used for final confirmation or in those laboratories where real-time facility/expertise is not existing. This study reports the development and optimization of nested RT-PCR and a TaqMan-based real-time PCR for Malsoor virus and AdV. The diagnostic assays can be used for rapid detection of these novel viruses to understand their prevalence among bat population.

Role of external neutrons of weakly bound nuclei in reactions with their participation

NASA Astrophysics Data System (ADS)

Naumenko, M. A.; Penionzhkevich, Yu E.; Samarin, V. V.; Sobolev, Yu G.

2018-05-01

The paper presents the results of measurement of the total cross sections for reactions 4,6He+Si and 6,7,9Li+Si in the beam energy range 5–50 A MeV. The enhancements of the total cross sections for reaction 6He+Si compared with reaction 4He+Si and 9Li+Si compared with reactions 6,7Li+Si have been observed. The performed microscopic analysis of total cross sections for reactions 6He+Si and 9Li+Si based on numerical solution of the time-dependent Schrödinger equation for external neutrons of projectile nuclei 6He and 9Li yielded good agreement with experimental data.

Silica hydride intermediate for octadecylsilica and phenyl bonded phase preparation via heterogeneous hydrosilation in supercritical carbon dioxide.

PubMed

Scully, N M; Ashu-Arrah, B A; Nagle, A P; Omamogho, J O; O'Sullivan, G P; Friebolin, V; Dietrich, B; Albert, K; Glennon, J D

2011-04-15

Investigations into the preparation of silica hydride intermediate in supercritical carbon dioxide (sc-CO(2)) that avoids the use of organic solvents such as toluene or dioxane are described. The effects of reaction temperature, pressure and time on the surface coverage of the supercritical fluid generated silica hydride intermediate were studied. Under optimised supercritical conditions of 120°C, 483 bar and 3 h reaction time, silica hydride (Si-H) conversion efficiencies of ca. 40% were achieved for the hydride intermediate prepared from a monofunctional silane reagent (dimethylmethoxysilane). Si-H conversion efficiencies (as determined from (29)Si CP-MAS NMR spectral analysis) for the hydride intermediate prepared from triethoxysilane (TES) in sc-CO(2) were found to be comparable to those obtained using a TES silanisation approach in an organic solvent. (13)C and (29)Si CP-MAS-NMR spectroscopy was employed to provide a complete structural assignment of the silica hydride intermediates. Furthermore, supercritical CO(2) was subsequently employed as a reaction medium for the heterogenous hydrosilation of silica hydride with octadecene and with styrene, in the presence of a free radical initiator. These supercritical fluid generated reversed-phase materials were prepared in a substantially reduced reaction time (3 h) compared to organic solvent based methods (100 h reaction time). Silica functionalisation in sc-CO(2) presents an efficient and clean alternative to organic solvent based methods for the preparation of important silica hydride intermediate and silica bonded stationary phases via a hydrosilation approach. Copyright © 2010 Elsevier B.V. All rights reserved.

Predictor - Predictive Reaction Design via Informatics, Computation and Theories of Reactivity

DTIC Science & Technology

2017-10-10

into more complex and valuable molecules, but are limited by: 1. The extensive time it takes to design and optimize a synthesis 2. Multi-step...system. As it is fully compatible to the industry standard SQL, designing a server- based system at a later time will be trivial. Producing a JAVA front...Report: PREDICTOR - Predictive REaction Design via Informatics, Computation and Theories of Reactivity The goal of this program was to create a cyber

Mechanistic Kinetic Modeling of Thiol-Michael Addition Photopolymerizations via Photocaged "Superbase" Generators: An Analytical Approach.

PubMed

Claudino, Mauro; Zhang, Xinpeng; Alim, Marvin D; Podgórski, Maciej; Bowman, Christopher N

2016-11-08

A kinetic mechanism and the accompanying mathematical framework are presented for base-mediated thiol-Michael photopolymerization kinetics involving a photobase generator. Here, model kinetic predictions demonstrate excellent agreement with a representative experimental system composed of 2-(2-nitrophenyl)propyloxycarbonyl-1,1,3,3-tetramethylguanidine (NPPOC-TMG) as a photobase generator that is used to initiate thiol-vinyl sulfone Michael addition reactions and polymerizations. Modeling equations derived from a basic mechanistic scheme indicate overall polymerization rates that follow a pseudo-first-order kinetic process in the base and coreactant concentrations, controlled by the ratio of the propagation to chain-transfer kinetic parameters ( k p / k CT ) which is dictated by the rate-limiting step and controls the time necessary to reach gelation. Gelation occurs earlier as the k p / k CT ratio reaches a critical value, wherefrom gel times become nearly independent of k p / k CT . The theoretical approach allowed determining the effect of induction time on the reaction kinetics due to initial acid-base neutralization for the photogenerated base caused by the presence of protic contaminants. Such inhibition kinetics may be challenging for reaction systems that require high curing rates but are relevant for chemical systems that need to remain kinetically dormant until activated although at the ultimate cost of lower polymerization rates. The pure step-growth character of this living polymerization and the exhibited kinetics provide unique potential for extended dark-cure reactions and uniform material properties. The general kinetic model is applicable to photobase initiators where photolysis follows a unimolecular cleavage process releasing a strong base catalyst without cogeneration of intermediate radical species.

Spectroscopic characteristics of carbon dots (C-dots) derived from carbon fibers and conversion to sulfur-bridged C-dots nanosheets.

PubMed

Vinci, John C; Ferrer, Ivonne M; Guterry, Nathan W; Colón, Verónica M; Destino, Joel F; Bright, Frank V; Colón, Luis A

2015-09-01

We synthesized sub-10 nm carbon nanoparticles (CNPs) consistent with photoluminescent carbon dots (C-dots) from carbon fiber starting material. The production of different C-dots fractions was monitored over seven days. During the course of the reaction, one fraction of C-dots species with relatively high photoluminescence was short-lived, emerging during the first hour of reaction but disappearing after one day of reaction. Isolation of this species during the first hour of the reaction was crucial to obtaining higher-luminescent C-dots species. When the reaction proceeded for one week, the appearance of larger nanostructures was observed over time, with lateral dimensions approaching 200 nm. The experimental evidence suggests that these larger species are formed from small C-dot nanoparticles bridged together by sulfur-based moieties between the C-dot edge groups, as if the C-dots polymerized by cross-linking the edge groups through sulfur bridges. Their size can be tailored by controlling the reaction time. Our results highlight the variety of CNP products, from sub-10 nm C-dots to ~200 nm sulfur-containing carbon nanostructures, that can be produced over time during the oxidation reaction of the graphenic starting material. Our work provides a clear understanding of when to stop the oxidation reaction during the top-down production of C-dots to obtain highly photoluminescent species or a target average particle size.

Confining Domains Lead to Reaction Bursts: Reaction Kinetics in the Plasma Membrane

PubMed Central

Kalay, Ziya; Fujiwara, Takahiro K.; Kusumi, Akihiro

2012-01-01

Confinement of molecules in specific small volumes and areas within a cell is likely to be a general strategy that is developed during evolution for regulating the interactions and functions of biomolecules. The cellular plasma membrane, which is the outermost membrane that surrounds the entire cell, was considered to be a continuous two-dimensional liquid, but it is becoming clear that it consists of numerous nano-meso-scale domains with various lifetimes, such as raft domains and cytoskeleton-induced compartments, and membrane molecules are dynamically trapped in these domains. In this article, we give a theoretical account on the effects of molecular confinement on reversible bimolecular reactions in a partitioned surface such as the plasma membrane. By performing simulations based on a lattice-based model of diffusion and reaction, we found that in the presence of membrane partitioning, bimolecular reactions that occur in each compartment proceed in bursts during which the reaction rate is sharply and briefly increased even though the asymptotic reaction rate remains the same. We characterized the time between reaction bursts and the burst amplitude as a function of the model parameters, and discussed the biological significance of the reaction bursts in the presence of strong inhibitor activity. PMID:22479350

Thermal explosion violence of HMX-based explosives -- effect of composition, confinement and phase transition using the scaled thermal explosion experiment

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

Maienschein, J L; Wardell, J F; Reaugh, J E

We developed the Scaled Thermal Explosion Experiment (STEX) to provide a database of reaction violence from thermal explosion of explosives of interest. A cylinder of explosive, 1, 2 or 4 inches in diameter, is confined in a steel cylinder with heavy end caps, and heated under controlled conditions until it explodes. Reaction violence is quantified by micropower radar measurement of the cylinder wall velocity, and by strain gauge data at reaction onset. Here we describe the test concept and design, show that the conditions are well understood, and present initial data with HMX-based explosives. The HMX results show that anmore » explosive with high binder content yields less-violent reactions that an explosive with low binder content, and that the HMX phase at the time of explosion plays a key role in reaction violence.« less

A comparative study of visual reaction time in table tennis players and healthy controls.

PubMed

Bhabhor, Mahesh K; Vidja, Kalpesh; Bhanderi, Priti; Dodhia, Shital; Kathrotia, Rajesh; Joshi, Varsha

2013-01-01

Visual reaction time is time required to response to visual stimuli. The present study was conducted to measure visual reaction time in 209 subjects, 50 table tennis (TT) players and 159 healthy controls. The visual reaction time was measured by the direct RT computerized software in healthy controls and table tennis players. Simple visual reaction time was measured. During the reaction time testing, visual stimuli were given for eighteen times and average reaction time was taken as the final reaction time. The study shows that table tennis players had faster reaction time than healthy controls. On multivariate analysis, it was found that TT players had 74.121 sec (95% CI 98.8 and 49.4 sec) faster reaction time compared to non-TT players of same age and BMI. Also playing TT has a profound influence on visual reaction time than BMI. Our study concluded that persons involved in sports are having good reaction time as compared to controls. These results support the view that playing of table tennis is beneficial to eye-hand reaction time, improve the concentration and alertness.

Time-based understanding of DLCO and DLNO.

PubMed

Kang, Min-Yeong; Sapoval, Bernard

2016-05-01

Capture of CO and NO by blood requires molecules to travel by diffusion from alveolar gas to haemoglobin molecules inside RBCs and then to react. One can attach to these processes two times, a time for diffusion and a time for reaction. This reaction time is known from chemical kinetics and, therefore, constitutes a unique physical clock. This paper presents a time-based bottom-up theory that yields a simple expression for DLCO and DLNO that produces quantitative predictions which compare successfully with experiments. Specifically, when this new approach is applied to DLCO experiments, it can be used to determine the value of the characteristic diffusion time, and the value of capillary volume (Vc). The new theory also provides a simple explanation for still unexplained correlations such as the observed proportionality between the so-called membrane conductance DM and Vc of Roughton and Forster's interpretation. This new theory indicates that DLCO should be proportional to the haematocrit as found in several experiments. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Kinetics of Ethyl Acetate Synthesis Catalyzed by Acidic Resins

ERIC Educational Resources Information Center

Antunes, Bruno M.; Cardoso, Simao P.; Silva, Carlos M.; Portugal, Ines

2011-01-01

A low-cost experiment to carry out the second-order reversible reaction of acetic acid esterification with ethanol to produce ethyl acetate is presented to illustrate concepts of kinetics and reactor modeling. The reaction is performed in a batch reactor, and the acetic acid concentration is measured by acid-base titration versus time. The…

Multiplexed immunosensing and kinetics monitoring in nanofluidic devices with highly enhanced target capture efficiency

PubMed Central

Lin, Yii-Lih; Huang, Yen-Jun; Teerapanich, Pattamon; Leïchlé, Thierry

2016-01-01

Nanofluidic devices promise high reaction efficiency and fast kinetic responses due to the spatial constriction of transported biomolecules with confined molecular diffusion. However, parallel detection of multiple biomolecules, particularly proteins, in highly confined space remains challenging. This study integrates extended nanofluidics with embedded protein microarray to achieve multiplexed real-time biosensing and kinetics monitoring. Implementation of embedded standard-sized antibody microarray is attained by epoxy-silane surface modification and a room-temperature low-aspect-ratio bonding technique. An effective sample transport is achieved by electrokinetic pumping via electroosmotic flow. Through the nanoslit-based spatial confinement, the antigen-antibody binding reaction is enhanced with ∼100% efficiency and may be directly observed with fluorescence microscopy without the requirement of intermediate washing steps. The image-based data provide numerous spatially distributed reaction kinetic curves and are collectively modeled using a simple one-dimensional convection-reaction model. This study represents an integrated nanofluidic solution for real-time multiplexed immunosensing and kinetics monitoring, starting from device fabrication, protein immobilization, device bonding, sample transport, to data analysis at Péclet number less than 1. PMID:27375819

Development and application of a tyrosinase-based time-temperature indicator (TTI) for determining the quality of turbot sashimi

NASA Astrophysics Data System (ADS)

Xu, Fengjuan; Ge, Lei; Li, Zhenxing; Lin, Hong; Mao, Xiangzhao

2017-10-01

Time-temperature indicators (TTIs) are convenient intuitive devices that are widely used to predict food quality. The aim of this study is to develop a new simple device which can be attached to food packages as a quality indicator for turbot sashimi. In this study, a solid TTI based on the reaction between tyrosinase and tyrosine was developed. The Arrhenius behavior of this enzymatic TTI was studied. The kinetics of the tyrosinase-based TTI was investigated in the form of color change from colorless to dark black induced by the enzymatic reaction. The mathematical formula for the color alterations as a function of time and temperature was established. The longest indication time for the developed TTI was 50 hours at 4°C. The activation energy of the tyrosinase-based TTI was 0.409 kJ mol-1. The suitability of the tyrosinase-based TTI was validated for turbot sashimi using total plate count. The feasibility of using this TTI as a quality indicator for turbot sashimi was assessed based on the activation energy and indication time. Therefore, the tyrosinasebased TTI system developed in this study could be used as an effective tool for monitoring the quality changes of turbot sashimi during the distribution and storage.

Reaction dynamics analysis of a reconstituted Escherichia coli protein translation system by computational modeling

PubMed Central

Matsuura, Tomoaki; Tanimura, Naoki; Hosoda, Kazufumi; Yomo, Tetsuya; Shimizu, Yoshihiro

2017-01-01

To elucidate the dynamic features of a biologically relevant large-scale reaction network, we constructed a computational model of minimal protein synthesis consisting of 241 components and 968 reactions that synthesize the Met-Gly-Gly (MGG) peptide based on an Escherichia coli-based reconstituted in vitro protein synthesis system. We performed a simulation using parameters collected primarily from the literature and found that the rate of MGG peptide synthesis becomes nearly constant in minutes, thus achieving a steady state similar to experimental observations. In addition, concentration changes to 70% of the components, including intermediates, reached a plateau in a few minutes. However, the concentration change of each component exhibits several temporal plateaus, or a quasi-stationary state (QSS), before reaching the final plateau. To understand these complex dynamics, we focused on whether the components reached a QSS, mapped the arrangement of components in a QSS in the entire reaction network structure, and investigated time-dependent changes. We found that components in a QSS form clusters that grow over time but not in a linear fashion, and that this process involves the collapse and regrowth of clusters before the formation of a final large single cluster. These observations might commonly occur in other large-scale biological reaction networks. This developed analysis might be useful for understanding large-scale biological reactions by visualizing complex dynamics, thereby extracting the characteristics of the reaction network, including phase transitions. PMID:28167777

Evaluation and linking of effective parameters in particle-based models and continuum models for mixing-limited bimolecular reactions

NASA Astrophysics Data System (ADS)

Zhang, Yong; Papelis, Charalambos; Sun, Pengtao; Yu, Zhongbo

2013-08-01

Particle-based models and continuum models have been developed to quantify mixing-limited bimolecular reactions for decades. Effective model parameters control reaction kinetics, but the relationship between the particle-based model parameter (such as the interaction radius R) and the continuum model parameter (i.e., the effective rate coefficient Kf) remains obscure. This study attempts to evaluate and link R and Kf for the second-order bimolecular reaction in both the bulk and the sharp-concentration-gradient (SCG) systems. First, in the bulk system, the agent-based method reveals that R remains constant for irreversible reactions and decreases nonlinearly in time for a reversible reaction, while mathematical analysis shows that Kf transitions from an exponential to a power-law function. Qualitative link between R and Kf can then be built for the irreversible reaction with equal initial reactant concentrations. Second, in the SCG system with a reaction interface, numerical experiments show that when R and Kf decline as t-1/2 (for example, to account for the reactant front expansion), the two models capture the transient power-law growth of product mass, and their effective parameters have the same functional form. Finally, revisiting of laboratory experiments further shows that the best fit factor in R and Kf is on the same order, and both models can efficiently describe chemical kinetics observed in the SCG system. Effective model parameters used to describe reaction kinetics therefore may be linked directly, where the exact linkage may depend on the chemical and physical properties of the system.

Enzymatic synthesis of chiral amino-alcohols by coupling transketolase and transaminase-catalyzed reactions in a cascading continuous-flow microreactor system.

PubMed

Gruber, Pia; Carvalho, Filipe; Marques, Marco P C; O'Sullivan, Brian; Subrizi, Fabiana; Dobrijevic, Dragana; Ward, John; Hailes, Helen C; Fernandes, Pedro; Wohlgemuth, Roland; Baganz, Frank; Szita, Nicolas

2018-03-01

Rapid biocatalytic process development and intensification continues to be challenging with currently available methods. Chiral amino-alcohols are of particular interest as they represent key industrial synthons for the production of complex molecules and optically pure pharmaceuticals. (2S,3R)-2-amino-1,3,4-butanetriol (ABT), a building block for the synthesis of protease inhibitors and detoxifying agents, can be synthesized from simple, non-chiral starting materials, by coupling a transketolase- and a transaminase-catalyzed reaction. However, until today, full conversion has not been shown and, typically, long reaction times are reported, making process modifications and improvement challenging. In this contribution, we present a novel microreactor-based approach based on free enzymes, and we report for the first time full conversion of ABT in a coupled enzyme cascade for both batch and continuous-flow systems. Using the compartmentalization of the reactions afforded by the microreactor cascade, we overcame inhibitory effects, increased the activity per unit volume, and optimized individual reaction conditions. The transketolase-catalyzed reaction was completed in under 10 min with a volumetric activity of 3.25 U ml -1 . Following optimization of the transaminase-catalyzed reaction, a volumetric activity of 10.8 U ml -1 was attained which led to full conversion of the coupled reaction in 2 hr. The presented approach illustrates how continuous-flow microreactors can be applied for the design and optimization of biocatalytic processes. © 2017 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals, Inc.

A DFT-Based Computational-Experimental Methodology for Synthetic Chemistry: Example of Application to the Catalytic Opening of Epoxides by Titanocene.

PubMed

Jaraíz, Martín; Enríquez, Lourdes; Pinacho, Ruth; Rubio, José E; Lesarri, Alberto; López-Pérez, José L

2017-04-07

A novel DFT-based Reaction Kinetics (DFT-RK) simulation approach, employed in combination with real-time data from reaction monitoring instrumentation (like UV-vis, FTIR, Raman, and 2D NMR benchtop spectrometers), is shown to provide a detailed methodology for the analysis and design of complex synthetic chemistry schemes. As an example, it is applied to the opening of epoxides by titanocene in THF, a catalytic system with abundant experimental data available. Through a DFT-RK analysis of real-time IR data, we have developed a comprehensive mechanistic model that opens new perspectives to understand previous experiments. Although derived specifically from the opening of epoxides, the prediction capabilities of the model, built on elementary reactions, together with its practical side (reaction kinetics simulations of real experimental conditions) make it a useful simulation tool for the design of new experiments, as well as for the conception and development of improved versions of the reagents. From the perspective of the methodology employed, because both the computational (DFT-RK) and the experimental (spectroscopic data) components can follow the time evolution of several species simultaneously, it is expected to provide a helpful tool for the study of complex systems in synthetic chemistry.

Estimating reaction rate coefficients within a travel-time modeling framework.

PubMed

Gong, R; Lu, C; Wu, W-M; Cheng, H; Gu, B; Watson, D; Jardine, P M; Brooks, S C; Criddle, C S; Kitanidis, P K; Luo, J

2011-01-01

A generalized, efficient, and practical approach based on the travel-time modeling framework is developed to estimate in situ reaction rate coefficients for groundwater remediation in heterogeneous aquifers. The required information for this approach can be obtained by conducting tracer tests with injection of a mixture of conservative and reactive tracers and measurements of both breakthrough curves (BTCs). The conservative BTC is used to infer the travel-time distribution from the injection point to the observation point. For advection-dominant reactive transport with well-mixed reactive species and a constant travel-time distribution, the reactive BTC is obtained by integrating the solutions to advective-reactive transport over the entire travel-time distribution, and then is used in optimization to determine the in situ reaction rate coefficients. By directly working on the conservative and reactive BTCs, this approach avoids costly aquifer characterization and improves the estimation for transport in heterogeneous aquifers which may not be sufficiently described by traditional mechanistic transport models with constant transport parameters. Simplified schemes are proposed for reactive transport with zero-, first-, nth-order, and Michaelis-Menten reactions. The proposed approach is validated by a reactive transport case in a two-dimensional synthetic heterogeneous aquifer and a field-scale bioremediation experiment conducted at Oak Ridge, Tennessee. The field application indicates that ethanol degradation for U(VI)-bioremediation is better approximated by zero-order reaction kinetics than first-order reaction kinetics. Copyright © 2010 The Author(s). Journal compilation © 2010 National Ground Water Association.

Estimating Reaction Rate Coefficients Within a Travel-Time Modeling Framework

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

Gong, R; Lu, C; Luo, Jian

A generalized, efficient, and practical approach based on the travel-time modeling framework is developed to estimate in situ reaction rate coefficients for groundwater remediation in heterogeneous aquifers. The required information for this approach can be obtained by conducting tracer tests with injection of a mixture of conservative and reactive tracers and measurements of both breakthrough curves (BTCs). The conservative BTC is used to infer the travel-time distribution from the injection point to the observation point. For advection-dominant reactive transport with well-mixed reactive species and a constant travel-time distribution, the reactive BTC is obtained by integrating the solutions to advective-reactive transportmore » over the entire travel-time distribution, and then is used in optimization to determine the in situ reaction rate coefficients. By directly working on the conservative and reactive BTCs, this approach avoids costly aquifer characterization and improves the estimation for transport in heterogeneous aquifers which may not be sufficiently described by traditional mechanistic transport models with constant transport parameters. Simplified schemes are proposed for reactive transport with zero-, first-, nth-order, and Michaelis-Menten reactions. The proposed approach is validated by a reactive transport case in a two-dimensional synthetic heterogeneous aquifer and a field-scale bioremediation experiment conducted at Oak Ridge, Tennessee. The field application indicates that ethanol degradation for U(VI)-bioremediation is better approximated by zero-order reaction kinetics than first-order reaction kinetics.« less

A new perspective on binaural integration using response time methodology: super capacity revealed in conditions of binaural masking release.

PubMed

Lentz, Jennifer J; He, Yuan; Townsend, James T

2014-01-01

This study applied reaction-time based methods to assess the workload capacity of binaural integration by comparing reaction time (RT) distributions for monaural and binaural tone-in-noise detection tasks. In the diotic contexts, an identical tone + noise stimulus was presented to each ear. In the dichotic contexts, an identical noise was presented to each ear, but the tone was presented to one of the ears 180° out of phase with respect to the other ear. Accuracy-based measurements have demonstrated a much lower signal detection threshold for the dichotic vs. the diotic conditions, but accuracy-based techniques do not allow for assessment of system dynamics or resource allocation across time. Further, RTs allow comparisons between these conditions at the same signal-to-noise ratio. Here, we apply a reaction-time based capacity coefficient, which provides an index of workload efficiency and quantifies the resource allocations for single ear vs. two ear presentations. We demonstrate that the release from masking generated by the addition of an identical stimulus to one ear is limited-to-unlimited capacity (efficiency typically less than 1), consistent with less gain than would be expected by probability summation. However, the dichotic presentation leads to a significant increase in workload capacity (increased efficiency)-most specifically at lower signal-to-noise ratios. These experimental results provide further evidence that configural processing plays a critical role in binaural masking release, and that these mechanisms may operate more strongly when the signal stimulus is difficult to detect, albeit still with nearly 100% accuracy.

A new perspective on binaural integration using response time methodology: super capacity revealed in conditions of binaural masking release

PubMed Central

Lentz, Jennifer J.; He, Yuan; Townsend, James T.

2014-01-01

This study applied reaction-time based methods to assess the workload capacity of binaural integration by comparing reaction time (RT) distributions for monaural and binaural tone-in-noise detection tasks. In the diotic contexts, an identical tone + noise stimulus was presented to each ear. In the dichotic contexts, an identical noise was presented to each ear, but the tone was presented to one of the ears 180° out of phase with respect to the other ear. Accuracy-based measurements have demonstrated a much lower signal detection threshold for the dichotic vs. the diotic conditions, but accuracy-based techniques do not allow for assessment of system dynamics or resource allocation across time. Further, RTs allow comparisons between these conditions at the same signal-to-noise ratio. Here, we apply a reaction-time based capacity coefficient, which provides an index of workload efficiency and quantifies the resource allocations for single ear vs. two ear presentations. We demonstrate that the release from masking generated by the addition of an identical stimulus to one ear is limited-to-unlimited capacity (efficiency typically less than 1), consistent with less gain than would be expected by probability summation. However, the dichotic presentation leads to a significant increase in workload capacity (increased efficiency)—most specifically at lower signal-to-noise ratios. These experimental results provide further evidence that configural processing plays a critical role in binaural masking release, and that these mechanisms may operate more strongly when the signal stimulus is difficult to detect, albeit still with nearly 100% accuracy. PMID:25202254

Neural network modeling of the kinetics of SO2 removal by fly ash-based sorbent.

PubMed

Raymond-Ooi, E H; Lee, K T; Mohamed, A R; Chu, K H

2006-01-01

The mechanistic modeling of the sulfation reaction between fly ash-based sorbent and SO2 is a challenging task due to a variety reasons including the complexity of the reaction itself and the inability to measure some of the key parameters of the reaction. In this work, the possibility of modeling the sulfation reaction kinetics using a purely data-driven neural network was investigated. Experiments on SO2 removal by a sorbent prepared from coal fly ash/CaO/CaSO4 were conducted using a fixed bed reactor to generate a database to train and validate the neural network model. Extensive SO2 removal data points were obtained by varying three process variables, namely, SO2 inlet concentration (500-2000 mg/L), reaction temperature (60-80 degreesC), and relative humidity (50-70%), as a function of reaction time (0-60 min). Modeling results show that the neural network can provide excellent fits to the SO2 removal data after considerable training and can be successfully used to predict the extent of SO2 removal as a function of time even when the process variables are outside the training domain. From a modeling standpoint, the suitably trained and validated neural network with excellent interpolation and extrapolation properties could have immediate practical benefits in the absence of a theoretical model.

Transesterification of waste vegetable oil under pulse sonication using ethanol, methanol and ethanol-methanol mixtures.

PubMed

Martinez-Guerra, Edith; Gude, Veera Gnaneswar

2014-12-01

This study reports on the effects of direct pulse sonication and the type of alcohol (methanol and ethanol) on the transesterification reaction of waste vegetable oil without any external heating or mechanical mixing. Biodiesel yields and optimum process conditions for the transesterification reaction involving ethanol, methanol, and ethanol-methanol mixtures were evaluated. The effects of ultrasonic power densities (by varying sample volumes), power output rates (in W), and ultrasonic intensities (by varying the reactor size) were studied for transesterification reaction with ethanol, methanol and ethanol-methanol (50%-50%) mixtures. The optimum process conditions for ethanol or methanol based transesterification reaction of waste vegetable oil were determined as: 9:1 alcohol to oil ratio, 1% wt. catalyst amount, 1-2 min reaction time at a power output rate between 75 and 150 W. It was shown that the transesterification reactions using ethanol-methanol mixtures resulted in biodiesel yields as high as >99% at lower power density and ultrasound intensity when compared to ethanol or methanol based transesterification reactions. Copyright © 2014 Elsevier Ltd. All rights reserved.

The sound of a mobile phone ringing affects the complex reaction time of its owner

PubMed Central

Zajdel, Justyna; Zwolińska, Anna; Śmigielski, Janusz; Beling, Piotr; Cegliński, Tomasz; Nowak, Dariusz

2012-01-01

Introduction Mobile phone conversation decreases the ability to concentrate and impairs the attention necessary to perform complex activities, such as driving a car. Does the ringing sound of a mobile phone affect the driver's ability to perform complex sensory-motor activities? We compared a subject's reaction time while performing a test either with a mobile phone ringing or without. Material and methods The examination was performed on a PC-based reaction time self-constructed system Reactor. The study group consisted of 42 healthy students. The protocol included instruction, control without phone and a proper session with subject's mobile phone ringing. The terms of the study were standardised. Results There were significant differences (p < 0.001) in reaction time in control (597 ms), mobile (633 ms) and instruction session (673 ms). The differences in female subpopulation were also significant (p < 0.01). Women revealed the longest reaction time in instruction session (707 ms), were significantly quicker in mobile (657 ms, p < 0.01) and in control session (612 ms, p < 0.001). In men, the significant difference was recorded only between instruction (622 ms) and control session (573 ms, p < 0.01). The other differences were not significant (p > 0.08). Men proofed to complete significantly quicker than women in instruction (p < 0.01) and in mobile session (p < 0.05). Differences amongst the genders in control session was not significant (p > 0.05). Conclusions The results obtained proofed the ringing of a phone exerts a significant influence on complex reaction time and quality of performed task. PMID:23185201

The effect of self-regulated caffeine use on cognition in young adults.

PubMed

Harvanko, Arit M; Derbyshire, Katherine L; Schreiber, Liana R N; Grant, Jon E

2015-03-01

Based on previous observational studies that have suggested self-regulated caffeine use by older adults may enhance reaction time performance and vigilance on cognitive tasks, the current study sought to examine whether this effect held true for young adults as well. One hundred and four young adults from two major metropolitan areas, ages 18-29 years, not meeting the criteria for a current psychiatric disorder, completed several cognitive tasks related to decision-making (Cambridge Gamble Task), response inhibition and reaction time (stop-signal task), and vigilance and reaction time (Rapid Visual Information Processing). Caffeine usage was self-reported using a reliable quantity and frequency questionnaire. Self-reported caffeine usage was not significantly associated with any of the cognitive measures used in this study after controlling for age, gender, cigarette smoking, alcohol use, cannabis use, and gambling frequency. These data suggest that self-regulated caffeine usage may not have a significant impact on reaction time, vigilance, response inhibition, or decision-making in young adults, or that these effects are contingent upon other variables not accounted for in the current study. Copyright © 2015 John Wiley & Sons, Ltd.

Time-resolved vibrational spectroscopy detects protein-based intermediates in the photosynthetic oxygen-evolving cycle.

PubMed

Barry, Bridgette A; Cooper, Ian B; De Riso, Antonio; Brewer, Scott H; Vu, Dung M; Dyer, R Brian

2006-05-09

Photosynthetic oxygen production by photosystem II (PSII) is responsible for the maintenance of aerobic life on earth. The production of oxygen occurs at the PSII oxygen-evolving complex (OEC), which contains a tetranuclear manganese (Mn) cluster. Photo-induced electron transfer events in the reaction center lead to the accumulation of oxidizing equivalents on the OEC. Four sequential photooxidation reactions are required for oxygen production. The oxidizing complex cycles among five oxidation states, called the S(n) states, where n refers to the number of oxidizing equivalents stored. Oxygen release occurs during the S(3)-to-S(0) transition from an unstable intermediate, known as the S(4) state. In this report, we present data providing evidence for the production of an intermediate during each S state transition. These protein-derived intermediates are produced on the microsecond to millisecond time scale and are detected by time-resolved vibrational spectroscopy on the microsecond time scale. Our results suggest that a protein-derived conformational change or proton transfer reaction precedes Mn redox reactions during the S(2)-to-S(3) and S(3)-to-S(0) transitions.

Optimization of the performance of the polymerase chain reaction in silicon-based microstructures.

PubMed Central

Taylor, T B; Winn-Deen, E S; Picozza, E; Woudenberg, T M; Albin, M

1997-01-01

We have demonstrated the ability to perform real-time homogeneous, sequence specific detection of PCR products in silicon microstructures. Optimal design/ processing result in equivalent performance (yield and specificity) for high surface-to-volume silicon structures as compared to larger volume reactions in polypropylene tubes. Amplifications in volumes as small as 0.5 microl and thermal cycling times reduced as much as 5-fold from that of conventional systems have been demonstrated for the microstructures. PMID:9224619

Development of an accurate and high-throughput methodology for structural comprehension of chlorophylls derivatives. (I) Phytylated derivatives.

PubMed

Chen, Kewei; Ríos, José Julián; Pérez-Gálvez, Antonio; Roca, María

2015-08-07

Phytylated chlorophyll derivatives undergo specific oxidative reactions through the natural metabolism or during food processing or storage, and consequently pyro-, 13(2)-hydroxy-, 15(1)-hydroxy-lactone chlorophylls, and pheophytins (a and b) are originated. New analytical procedures have been developed here to reproduce controlled oxidation reactions that specifically, and in reasonable amounts, produce those natural target standards. At the same time and under the same conditions, 16 natural chlorophyll derivatives have been analyzed by APCI-HPLC-hrMS(2) and most of them by the first time. The combination of the high-resolution MS mode with powerful post-processing software has allowed the identification of new fragmentation patterns, characterizing specific product ions for some particular standards. In addition, new hypotheses and reaction mechanisms for the established MS(2)-based reactions have been proposed. As a general rule, the main product ions involve the phytyl and the propionic chains but the introduction of oxygenated functional groups at the isocyclic ring produces new and specific productions and at the same time inhibits some particular fragmentations. It is noteworthy that all b derivatives, except 15(1)-hydroxy-lactone compounds, undergo specific CO losses. We propose a new reaction mechanism based in the structural configuration of a and b chlorophyll derivatives that explain the exclusive CO fragmentation in all b series except for 15(1)-hydroxy-lactone b and all a series compounds. Copyright © 2015 Elsevier B.V. All rights reserved.

Microscopic approach based on a multiscale algebraic version of the resonating group model for radiative capture reactions

NASA Astrophysics Data System (ADS)

Solovyev, Alexander S.; Igashov, Sergey Yu.

2017-12-01

A microscopic approach to description of radiative capture reactions based on a multiscale algebraic version of the resonating group model is developed. The main idea of the approach is to expand wave functions of discrete spectrum and continuum for a nuclear system over different bases of the algebraic version of the resonating group model. These bases differ from each other by values of oscillator radius playing a role of scale parameter. This allows us in a unified way to calculate total and partial cross sections (astrophysical S factors) as well as branching ratio for the radiative capture reaction, to describe phase shifts for the colliding nuclei in the initial channel of the reaction, and at the same time to reproduce breakup thresholds of the final nucleus. The approach is applied to the theoretical study of the mirror 3H(α ,γ )7Li and 3He(α ,γ )7Be reactions, which are of great interest to nuclear astrophysics. The calculated results are compared with existing experimental data and with our previous calculations in the framework of the single-scale algebraic version of the resonating group model.

The effects of self-induced mood states on behavior and physiological arousal.

PubMed

Matheny, K B; Blue, F R

1977-10-01

The effects of reading emotionally loaded statements on behavioral tasks and physiological measures were investigated. Statements were constructed to arouse elation, depression, or neutrality. Ss were both pre- and posttested on Writing Speed, Reaction Time, Decision Time, and Spontaneous Verbalizations. Base rates were obtained for heart rate and galvanic skin response. Elation Ss significantly outperformed both Neutral and Depression Ss on the Reaction Time task. Scores for Neutral Ss fell between those of Elation and Depression Ss on three of the four behavioral measures. No significant differneces were found on the physiological measures.

Validating the Accuracy of Reaction Time Assessment on Computer-Based Tablet Devices.

PubMed

Schatz, Philip; Ybarra, Vincent; Leitner, Donald

2015-08-01

Computer-based assessment has evolved to tablet-based devices. Despite the availability of tablets and "apps," there is limited research validating their use. We documented timing delays between stimulus presentation and (simulated) touch response on iOS devices (3rd- and 4th-generation Apple iPads) and Android devices (Kindle Fire, Google Nexus, Samsung Galaxy) at response intervals of 100, 250, 500, and 1,000 milliseconds (ms). Results showed significantly greater timing error on Google Nexus and Samsung tablets (81-97 ms), than Kindle Fire and Apple iPads (27-33 ms). Within Apple devices, iOS 7 obtained significantly lower timing error than iOS 6. Simple reaction time (RT) trials (250 ms) on tablet devices represent 12% to 40% error (30-100 ms), depending on the device, which decreases considerably for choice RT trials (3-5% error at 1,000 ms). Results raise implications for using the same device for serial clinical assessment of RT using tablets, as well as the need for calibration of software and hardware. © The Author(s) 2015.

Long-term mass transfer and mixing-controlled reactions of a DNAPL plume from persistent residuals

NASA Astrophysics Data System (ADS)

Liu, Yuan; Illangasekare, Tissa H.; Kitanidis, Peter K.

2014-02-01

Understanding and being able to predict the long-term behavior of DNAPL (i.e., PCE and TCE) residuals after active remediation has ceased have become increasingly important as attention at many sites turns from aggressive remediation to monitored natural attenuation and long-term stewardship. However, plume behavior due to mass loading and reactions during these later phases is less studied as they involve large spatial and temporal scales. We apply both theoretical analysis and pore-scale simulations to investigate mass transfer from DNAPL residuals and subsequent reactions within the generated plume, and, in particular, to show the differences between early- and late-time behaviors of the plume. In the zone of entry of the DNAPL entrapment zone where the concentration boundary layer in the flowing groundwater has not fully developed, the pore-scale simulations confirm the past findings based on laboratory studies that the mass transfer increases as a power-law function of the Peclét number, and is enhanced due to reactions in the plume. Away from the entry zone and further down gradient, the long-term reactions are limited by the available additive and mixing in the porous medium, thereby behave considerably differently from the entry zone. For the reaction between the contaminant and an additive with intrinsic second-order bimolecular kinetics, the late-time reaction demonstrates a first-order decay macroscopically with respect to the mass of the limiting additive, not with respect to that of the contaminant. The late-time decay rate only depends on the intrinsic reaction rate and the solubility of the entrapped DNAPL. At the intermediate time, the additive decays exponentially with the square of time (t2), instead of time (t). Moreover, the intermediate decay rate also depends on the initial conditions, the spatial distribution of DNAPL residuals, and the effective dispersion coefficient.

Lack of correlation between reaction speed and analytical sensitivity in isothermal amplification reveals the value of digital methods for optimization: validation using digital real-time RT-LAMP

PubMed Central

Khorosheva, Eugenia M.; Karymov, Mikhail A.; Selck, David A.; Ismagilov, Rustem F.

2016-01-01

In this paper, we asked if it is possible to identify the best primers and reaction conditions based on improvements in reaction speed when optimizing isothermal reactions. We used digital single-molecule, real-time analyses of both speed and efficiency of isothermal amplification reactions, which revealed that improvements in the speed of isothermal amplification reactions did not always correlate with improvements in digital efficiency (the fraction of molecules that amplify) or with analytical sensitivity. However, we observed that the speeds of amplification for single-molecule (in a digital device) and multi-molecule (e.g. in a PCR well plate) formats always correlated for the same conditions. Also, digital efficiency correlated with the analytical sensitivity of the same reaction performed in a multi-molecule format. Our finding was supported experimentally with examples of primer design, the use or exclusion of loop primers in different combinations, and the use of different enzyme mixtures in one-step reverse-transcription loop-mediated amplification (RT-LAMP). Our results show that measuring the digital efficiency of amplification of single-template molecules allows quick, reliable comparisons of the analytical sensitivity of reactions under any two tested conditions, independent of the speeds of the isothermal amplification reactions. PMID:26358811

Enhancement of biodiesel production from marine alga, Scenedesmus sp. through in situ transesterification process associated with acidic catalyst.

PubMed

Kim, Ga Vin; Choi, Woonyong; Kang, Dohyung; Lee, Shinyoung; Lee, Hyeonyong

2014-01-01

The aim of this study was to increase the yield of biodiesel produced by Scenedesmus sp. through in situ transesterification by optimizing various process parameters. Based on the orthogonal matrix analysis for the acidic catalyst, the effects of the factors decreased in the order of reaction temperature (47.5%) > solvent quantity (26.7%) > reaction time (17.5%) > catalyst amount (8.3%). Based on a Taguchi analysis, the effects of the factors decreased in the order of solvent ratio (34.36%) > catalyst (28.62%) > time (19.72%) > temperature (17.32%). The overall biodiesel production appeared to be better using NaOH as an alkaline catalyst rather than using H2SO4 in an acidic process, at 55.07 ± 2.18% (based on lipid weight) versus 48.41 ± 0.21%. However, in considering the purified biodiesel, it was found that the acidic catalyst was approximately 2.5 times more efficient than the alkaline catalyst under the following optimal conditions: temperature of 70 °C (level 2), reaction time of 10 hrs (level 2), catalyst amount of 5% (level 3), and biomass to solvent ratio of 1 : 15 (level 2), respectively. These results clearly demonstrated that the acidic solvent, which combined oil extraction with in situ transesterification, was an effective catalyst for the production of high-quantity, high-quality biodiesel from a Scenedesmus sp.

A Kernel-based Lagrangian method for imperfectly-mixed chemical reactions

NASA Astrophysics Data System (ADS)

Schmidt, Michael J.; Pankavich, Stephen; Benson, David A.

2017-05-01

Current Lagrangian (particle-tracking) algorithms used to simulate diffusion-reaction equations must employ a certain number of particles to properly emulate the system dynamics-particularly for imperfectly-mixed systems. The number of particles is tied to the statistics of the initial concentration fields of the system at hand. Systems with shorter-range correlation and/or smaller concentration variance require more particles, potentially limiting the computational feasibility of the method. For the well-known problem of bimolecular reaction, we show that using kernel-based, rather than Dirac delta, particles can significantly reduce the required number of particles. We derive the fixed width of a Gaussian kernel for a given reduced number of particles that analytically eliminates the error between kernel and Dirac solutions at any specified time. We also show how to solve for the fixed kernel size by minimizing the squared differences between solutions over any given time interval. Numerical results show that the width of the kernel should be kept below about 12% of the domain size, and that the analytic equations used to derive kernel width suffer significantly from the neglect of higher-order moments. The simulations with a kernel width given by least squares minimization perform better than those made to match at one specific time. A heuristic time-variable kernel size, based on the previous results, performs on par with the least squares fixed kernel size.

Enhancement of Biodiesel Production from Marine Alga, Scenedesmus sp. through In Situ Transesterification Process Associated with Acidic Catalyst

PubMed Central

Kim, Ga Vin; Choi, WoonYong; Kang, DoHyung; Lee, ShinYoung; Lee, HyeonYong

2014-01-01

The aim of this study was to increase the yield of biodiesel produced by Scenedesmus sp. through in situ transesterification by optimizing various process parameters. Based on the orthogonal matrix analysis for the acidic catalyst, the effects of the factors decreased in the order of reaction temperature (47.5%) > solvent quantity (26.7%) > reaction time (17.5%) > catalyst amount (8.3%). Based on a Taguchi analysis, the effects of the factors decreased in the order of solvent ratio (34.36%) > catalyst (28.62%) > time (19.72%) > temperature (17.32%). The overall biodiesel production appeared to be better using NaOH as an alkaline catalyst rather than using H2SO4 in an acidic process, at 55.07 ± 2.18% (based on lipid weight) versus 48.41 ± 0.21%. However, in considering the purified biodiesel, it was found that the acidic catalyst was approximately 2.5 times more efficient than the alkaline catalyst under the following optimal conditions: temperature of 70°C (level 2), reaction time of 10 hrs (level 2), catalyst amount of 5% (level 3), and biomass to solvent ratio of 1 : 15 (level 2), respectively. These results clearly demonstrated that the acidic solvent, which combined oil extraction with in situ transesterification, was an effective catalyst for the production of high-quantity, high-quality biodiesel from a Scenedesmus sp. PMID:24689039

Jet-A reaction mechanism study for combustion application

NASA Technical Reports Server (NTRS)

Lee, Chi-Ming; Kundu, Krishna; Acosta, Waldo

1991-01-01

Simplified chemical kinetic reaction mechanisms for the combustion of Jet A fuel was studied. Initially, 40 reacting species and 118 elementary chemical reactions were chosen based on a literature review. Through a sensitivity analysis with the use of LSENS General Kinetics and Sensitivity Analysis Code, 16 species and 21 elementary chemical reactions were determined from this study. This mechanism is first justified by comparison of calculated ignition delay time with the available shock tube data, then it is validated by comparison of calculated emissions from the plug flow reactor code with in-house flame tube data.

Secondary organic aerosol formation from ozone-initiated reactions with nicotine and secondhand tobacco smoke

NASA Astrophysics Data System (ADS)

Sleiman, Mohamad; Destaillats, Hugo; Smith, Jared D.; Liu, Chen-Lin; Ahmed, Musahid; Wilson, Kevin R.; Gundel, Lara A.

2010-11-01

We used controlled laboratory experiments to evaluate the aerosol-forming potential of ozone reactions with nicotine and secondhand smoke. Special attention was devoted to real-time monitoring of the particle size distribution and chemical composition of SOA as they are believed to be key factors determining the toxicity of SOA. The experimental approach was based on using a vacuum ultraviolet photon ionization time-of-flight aerosol mass spectrometer (VUV-AMS), a scanning mobility particle sizer (SMPS) and off-line thermal desorption coupled to mass spectrometry (TD-GC-MS) for gas-phase byproducts analysis. Results showed that exposure of SHS to ozone induced the formation of ultrafine particles (<100 nm) that contained high molecular weight nitrogenated species ( m/ z 400-500), which can be due to accretion/acid-base reactions and formation of oligomers. In addition, nicotine was found to contribute significantly (with yields 4-9%) to the formation of secondary organic aerosol through reaction with ozone. The main constituents of the resulting SOA were tentatively identified and a reaction mechanism was proposed to elucidate their formation. These findings identify a new component of thirdhand smoke that is associated with the formation of ultrafine particles (UFP) through oxidative aging of secondhand smoke. The significance of this chemistry for indoor exposure and health effects is highlighted.

Towards understanding the kinetic behaviour and limitations in photo-induced copper(i) catalyzed azide-alkyne cycloaddition (CuAAC) reactions.

PubMed

El-Zaatari, Bassil M; Shete, Abhishek U; Adzima, Brian J; Kloxin, Christopher J

2016-09-14

The kinetic behaviour of the photo-induced copper(i) catalyzed azide-alkyne cycloaddition (CuAAC) reaction was studied in detail using real-time Fourier transform infrared (FTIR) spectroscopy on both a solvent-based monofunctional and a neat polymer network forming system. The results in the solvent-based system showed near first-order kinetics on copper and photoinitiator concentrations up to a threshold value in which the kinetics switch to zeroth-order. This kinetic shift shows that the photo-CuAAC reaction is not susceptible from side reactions such as copper disproportionation, copper(i) reduction, and radical termination at the early stages of the reaction. The overall reaction rate and conversion is highly dependent on the initial concentrations of photoinitiator and copper(ii) as well as their relative ratios. The conversion was decreased when an excess of photoinitiator was utilized compared to its threshold value. Interestingly, the reaction showed an induction period at relatively low intensities. The induction period is decreased by increasing light intensity and photoinitiator concentration. The reaction trends and limitations were further observed in a solventless polymer network forming system, exhibiting a similar copper and photoinitiator threshold behaviour.

Towards understanding the kinetic behaviour and limitations in photo-induced copper(I) catalyzed azide-alkyne cycloaddition (CuAAC) reactions

PubMed Central

El-Zaatari, Bassil M.; Shete, Abhishek U.; Adzima, Brian J.; Kloxin, Christopher J.

2016-01-01

The kinetic behaviour of the photo-induced copper(I) catalyzed azide—alkyne cycloaddition (CuAAC) reaction was studied in detail using real-time Fourier Transform Infrared Spectroscopy (FTIR) on both a solvent-based monofunctional and a neat polymer network forming system. The results in the solvent-based system showed near first-order kinetics on copper and photoinitiator concentrations up to a threshold value in which the kinetics switch to zeroth-order. This kinetic shift shows that the photo-CuAAC reaction is not suseptible from side reactions such as copper disproportionation, copper(I) reduction, and radical termination at the early stages of the reaction. The overall reaction rate and conversion is highly dependent on the initial concentrations of photoinitiator and copper(II), as well as their relative ratios. The conversion was decreased when an excess of photoinitiator was utilized compared to its threshold value. Interestingly, the reaction showed an induction period at relatively low intensities. The induction period is decreased by increasing light intensity, and photoinitiator concentration. The reaction trends and limitations were further observed in a solventless polymer network forming system, exhibiting a similar copper and photoinitiator threshold behaviour. PMID:27711587

Mechanisms underlying the influence of saliency on value-based decisions

PubMed Central

Chen, Xiaomo; Mihalas, Stefan; Niebur, Ernst; Stuphorn, Veit

2013-01-01

Objects in the environment differ in their low-level perceptual properties (e.g., how easily a fruit can be recognized) as well as in their subjective value (how tasty it is). We studied the influence of visual salience on value-based decisions using a two alternative forced choice task, in which human subjects rapidly chose items from a visual display. All targets were equally easy to detect. Nevertheless, both value and salience strongly affected choices made and reaction times. We analyzed the neuronal mechanisms underlying these behavioral effects using stochastic accumulator models, allowing us to characterize not only the averages of reaction times but their full distributions. Independent models without interaction between the possible choices failed to reproduce the observed choice behavior, while models with mutual inhibition between alternative choices produced much better results. Mutual inhibition thus is an important feature of the decision mechanism. Value influenced the amount of accumulation in all models. In contrast, increased salience could either lead to an earlier start (onset model) or to a higher rate (speed model) of accumulation. Both models explained the data from the choice trials equally well. However, salience also affected reaction times in no-choice trials in which only one item was present, as well as error trials. Only the onset model could explain the observed reaction time distributions of error trials and no-choice trials. In contrast, the speed model could not, irrespective of whether the rate increase resulted from more frequent accumulated quanta or from larger quanta. Visual salience thus likely provides an advantage in the onset, not in the processing speed, of value-based decision making. PMID:24167161

Liquefaction behaviors of bamboo residues in a glycerol-based solvent using microwave energy

Treesearch

Jiulong Xie; Chung-Yun Hse; Todd F. Shupe; Jinqiu Qi; Hui Pan

2014-01-01

Liquefaction of bamboo was performed in glycerol–methanol as co-solvent using microwave energy and was evaluated by characterizing the liquefied residues. High efficiency conversion of bamboo was achieved under mild reaction conditions. Liquefaction temperature and time interacted to affect the liquefaction reaction. Fourier transform infrared analyzes of the residues...

Centrifugal Microfluidic System for Nucleic Acid Amplification and Detection.

PubMed

Miao, Baogang; Peng, Niancai; Li, Lei; Li, Zheng; Hu, Fei; Zhang, Zengming; Wang, Chaohui

2015-11-04

We report here the development of a rapid PCR microfluidic system comprising a double-shaft turntable and centrifugal-based disc that rapidly drives the PCR mixture between chambers set at different temperatures, and the bidirectional flow improved the space utilization of the disc. Three heating resistors and thermistors maintained uniform, specific temperatures for the denaturation, annealing, and extension steps of the PCR. Infrared imaging showed that there was little thermal interference between reaction chambers; the system enabled the cycle number and reaction time of each step to be independently adjusted. To validate the function and efficiency of the centrifugal microfluidic system, a 350-base pair target gene from the hepatitis B virus was amplified and quantitated by fluorescence detection. By optimizing the cycling parameters, the reaction time was reduced to 32 min as compared to 120 min for a commercial PCR machine. DNA samples with concentrations ranging from 10 to 10⁶ copies/mL could be quantitatively analyzed using this system. This centrifugal-based microfluidic platform is a useful system and possesses industrialization potential that can be used for portable diagnostics.

Centrifugal Microfluidic System for Nucleic Acid Amplification and Detection

PubMed Central

Miao, Baogang; Peng, Niancai; Li, Lei; Li, Zheng; Hu, Fei; Zhang, Zengming; Wang, Chaohui

2015-01-01

We report here the development of a rapid PCR microfluidic system comprising a double-shaft turntable and centrifugal-based disc that rapidly drives the PCR mixture between chambers set at different temperatures, and the bidirectional flow improved the space utilization of the disc. Three heating resistors and thermistors maintained uniform, specific temperatures for the denaturation, annealing, and extension steps of the PCR. Infrared imaging showed that there was little thermal interference between reaction chambers; the system enabled the cycle number and reaction time of each step to be independently adjusted. To validate the function and efficiency of the centrifugal microfluidic system, a 350-base pair target gene from the hepatitis B virus was amplified and quantitated by fluorescence detection. By optimizing the cycling parameters, the reaction time was reduced to 32 min as compared to 120 min for a commercial PCR machine. DNA samples with concentrations ranging from 10 to 106 copies/mL could be quantitatively analyzed using this system. This centrifugal-based microfluidic platform is a useful system and possesses industrialization potential that can be used for portable diagnostics. PMID:26556354

A solvent replenishment solution for managing evaporation of biochemical reactions in air-matrix digital microfluidics devices.

PubMed

Jebrail, Mais J; Renzi, Ronald F; Sinha, Anupama; Van De Vreugde, Jim; Gondhalekar, Carmen; Ambriz, Cesar; Meagher, Robert J; Branda, Steven S

2015-01-07

Digital microfluidics (DMF) is a powerful technique for sample preparation and analysis for a broad range of biological and chemical applications. In many cases, it is desirable to carry out DMF on an open surface, such that the matrix surrounding the droplets is ambient air. However, the utility of the air-matrix DMF format has been severely limited by problems with droplet evaporation, especially when the droplet-based biochemical reactions require high temperatures for long periods of time. We present a simple solution for managing evaporation in air-matrix DMF: just-in-time replenishment of the reaction volume using droplets of solvent. We demonstrate that this solution enables DMF-mediated execution of several different biochemical reactions (RNA fragmentation, first-strand cDNA synthesis, and PCR) over a range of temperatures (4-95 °C) and incubation times (up to 1 h or more) without use of oil, humidifying chambers, or off-chip heating modules. Reaction volumes and temperatures were maintained roughly constant over the course of each experiment, such that the reaction kinetics and products generated by the air-matrix DMF device were comparable to those of conventional benchscale reactions. This simple yet effective solution for evaporation management is an important advance in developing air-matrix DMF for a wide variety of new, high-impact applications, particularly in the biomedical sciences.

A solvent replenishment solution for managing evaporation of biochemical reactions in air-matrix digital microfluidics devices

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

Jebrail, Mais J.; Renzi, Ronald F.; Sinha, Anupama

Digital microfluidics (DMF) is a powerful technique for sample preparation and analysis for a broad range of biological and chemical applications. In many cases, it is desirable to carry out DMF on an open surface, such that the matrix surrounding the droplets is ambient air. However, the utility of the air-matrix DMF format has been severely limited by problems with droplet evaporation, especially when the droplet-based biochemical reactions require high temperatures for long periods of time. We present a simple solution for managing evaporation in air-matrix DMF: just-in-time replenishment of the reaction volume using droplets of solvent. We demonstrate thatmore » this solution enables DMF-mediated execution of several different biochemical reactions (RNA fragmentation, first-strand cDNA synthesis, and PCR) over a range of temperatures (4–95 °C) and incubation times (up to 1 h or more) without use of oil, humidifying chambers, or off-chip heating modules. Reaction volumes and temperatures were maintained roughly constant over the course of each experiment, such that the reaction kinetics and products generated by the air-matrix DMF device were comparable to those of conventional benchscale reactions. As a result, this simple yet effective solution for evaporation management is an important advance in developing air-matrix DMF for a wide variety of new, high-impact applications, particularly in the biomedical sciences.« less

A solvent replenishment solution for managing evaporation of biochemical reactions in air-matrix digital microfluidics devices

DOE PAGES

Jebrail, Mais J.; Renzi, Ronald F.; Sinha, Anupama; ...

2014-10-01

Digital microfluidics (DMF) is a powerful technique for sample preparation and analysis for a broad range of biological and chemical applications. In many cases, it is desirable to carry out DMF on an open surface, such that the matrix surrounding the droplets is ambient air. However, the utility of the air-matrix DMF format has been severely limited by problems with droplet evaporation, especially when the droplet-based biochemical reactions require high temperatures for long periods of time. We present a simple solution for managing evaporation in air-matrix DMF: just-in-time replenishment of the reaction volume using droplets of solvent. We demonstrate thatmore » this solution enables DMF-mediated execution of several different biochemical reactions (RNA fragmentation, first-strand cDNA synthesis, and PCR) over a range of temperatures (4–95 °C) and incubation times (up to 1 h or more) without use of oil, humidifying chambers, or off-chip heating modules. Reaction volumes and temperatures were maintained roughly constant over the course of each experiment, such that the reaction kinetics and products generated by the air-matrix DMF device were comparable to those of conventional benchscale reactions. As a result, this simple yet effective solution for evaporation management is an important advance in developing air-matrix DMF for a wide variety of new, high-impact applications, particularly in the biomedical sciences.« less

[Metrological analysis of measuring systems in testing an anticipatory reaction to the position of a moving object].

PubMed

Aksiuta, E F; Ostashev, A V; Sergeev, E V; Aksiuta, V E

1997-01-01

The methods of the information (entropy) error theory were used to make a metrological analysis of the well-known commercial measuring systems for timing an anticipative reaction (AR) to the position of a moving object, which is based on the electromechanical, gas-discharge, and electron principles. The required accuracy of measurement was ascertained to be achieved only by using the systems based on the electron principle of moving object simulation and AR measurement.

Time-Frequency Cross Mutual Information Analysis of the Brain Functional Networks Underlying Multiclass Motor Imagery.

PubMed

Gong, Anmin; Liu, Jianping; Chen, Si; Fu, Yunfa

2018-01-01

To study the physiologic mechanism of the brain during different motor imagery (MI) tasks, the authors employed a method of brain-network modeling based on time-frequency cross mutual information obtained from 4-class (left hand, right hand, feet, and tongue) MI tasks recorded as brain-computer interface (BCI) electroencephalography data. The authors explored the brain network revealed by these MI tasks using statistical analysis and the analysis of topologic characteristics, and observed significant differences in the reaction level, reaction time, and activated target during 4-class MI tasks. There was a great difference in the reaction level between the execution and resting states during different tasks: the reaction level of the left-hand MI task was the greatest, followed by that of the right-hand, feet, and tongue MI tasks. The reaction time required to perform the tasks also differed: during the left-hand and right-hand MI tasks, the brain networks of subjects reacted promptly and strongly, but there was a delay during the feet and tongue MI task. Statistical analysis and the analysis of network topology revealed the target regions of the brain network during different MI processes. In conclusion, our findings suggest a new way to explain the neural mechanism behind MI.

A genetic variant within STS previously associated with inattention in boys with attention deficit hyperactivity disorder is associated with enhanced cognition in healthy adult males.

PubMed

Humby, Trevor; Fisher, Amelia; Allen, Christopher; Reynolds, Meghann; Hartman, Annette; Giegling, Ina; Rujescu, Dan; Davies, William

2017-03-01

The enzyme steroid sulfatase (STS) converts sulfated steroids to their non-sulfated forms. Deficiency for this enzyme is associated with inattention but preserved response control. The polymorphism rs17268988 within the X-linked STS gene is associated with inattentive, but not other, symptoms in boys with attention deficit hyperactivity disorder (ADHD). We initially tested whether rs17268988 genotype was associated with attention, response control, and underlying aspects of cognition, using questionnaires and neuropsychological tasks, in two independent cohorts of healthy adult males. In an additional analysis based upon existing data, the performance of mice with genetic or pharmacological manipulations of the STS axis under attentionally demanding conditions was investigated. G-allele carriers at rs17268988 exhibited reduced reaction time, enhanced attention, and reduced reaction time variability relative to C-allele carriers. Mice with genetic or pharmacological manipulations of the STS axis were shown to have perturbed reaction time variability. Our findings provide additional support for an association between rs17268988 genotype and attention, which may be partially mediated by reaction time variability; they also indicate that, in contrast to the situation in boys with ADHD, in healthy men, the G-allele at rs17268988 is associated with enhanced cognition. As reaction time variability is a predictor of well-being, rs17268988 genotype may represent a biomarker for long-term health.

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

Wemhoff, A P; Burnham, A K; Nichols III, A L

The reduction of the number of reactions in kinetic models for both the HMX beta-delta phase transition and thermal cookoff provides an attractive alternative to traditional multi-stage kinetic models due to reduced calibration effort requirements. In this study, we use the LLNL code ALE3D to provide calibrated kinetic parameters for a two-reaction bidirectional beta-delta HMX phase transition model based on Sandia Instrumented Thermal Ignition (SITI) and Scaled Thermal Explosion (STEX) temperature history curves, and a Prout-Tompkins cookoff model based on One-Dimensional Time to Explosion (ODTX) data. Results show that the two-reaction bidirectional beta-delta transition model presented here agrees as wellmore » with STEX and SITI temperature history curves as a reversible four-reaction Arrhenius model, yet requires an order of magnitude less computational effort. In addition, a single-reaction Prout-Tompkins model calibrated to ODTX data provides better agreement with ODTX data than a traditional multi-step Arrhenius model, and can contain up to 90% less chemistry-limited time steps for low-temperature ODTX simulations. Manual calibration methods for the Prout-Tompkins kinetics provide much better agreement with ODTX experimental data than parameters derived from Differential Scanning Calorimetry (DSC) measurements at atmospheric pressure. The predicted surface temperature at explosion for STEX cookoff simulations is a weak function of the cookoff model used, and a reduction of up to 15% of chemistry-limited time steps can be achieved by neglecting the beta-delta transition for this type of simulation. Finally, the inclusion of the beta-delta transition model in the overall kinetics model can affect the predicted time to explosion by 1% for the traditional multi-step Arrhenius approach, while up to 11% using a Prout-Tompkins cookoff model.« less

Application of global kinetic models to HMX beta-delta transition and cookoff processes.

PubMed

Wemhoff, Aaron P; Burnham, Alan K; Nichols, Albert L

2007-03-08

The reduction of the number of reactions in kinetic models for both the HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) beta-delta phase transition and thermal cookoff provides an attractive alternative to traditional multi-stage kinetic models due to reduced calibration effort requirements. In this study, we use the LLNL code ALE3D to provide calibrated kinetic parameters for a two-reaction bidirectional beta-delta HMX phase transition model based on Sandia instrumented thermal ignition (SITI) and scaled thermal explosion (STEX) temperature history curves, and a Prout-Tompkins cookoff model based on one-dimensional time to explosion (ODTX) data. Results show that the two-reaction bidirectional beta-delta transition model presented here agrees as well with STEX and SITI temperature history curves as a reversible four-reaction Arrhenius model yet requires an order of magnitude less computational effort. In addition, a single-reaction Prout-Tompkins model calibrated to ODTX data provides better agreement with ODTX data than a traditional multistep Arrhenius model and can contain up to 90% fewer chemistry-limited time steps for low-temperature ODTX simulations. Manual calibration methods for the Prout-Tompkins kinetics provide much better agreement with ODTX experimental data than parameters derived from differential scanning calorimetry (DSC) measurements at atmospheric pressure. The predicted surface temperature at explosion for STEX cookoff simulations is a weak function of the cookoff model used, and a reduction of up to 15% of chemistry-limited time steps can be achieved by neglecting the beta-delta transition for this type of simulation. Finally, the inclusion of the beta-delta transition model in the overall kinetics model can affect the predicted time to explosion by 1% for the traditional multistep Arrhenius approach, and up to 11% using a Prout-Tompkins cookoff model.

Eutectic salt catalyzed environmentally benign and highly efficient Biginelli reaction.

PubMed

Azizi, Najmadin; Dezfuli, Sahar; Hahsemi, Mohmmad Mahmoodi

2012-01-01

A simple deep eutectic solvent based on tin (II) chloride was used as a dual catalyst and environmentally benign reaction medium for an efficient synthesis of 3,4-dihydropyrimidin-2(1H)-one derivatives, from aromatic and aliphatic aldehydes, 1,3-dicarbonyl compounds, and urea in good-to-excellent yields and short reaction time. This simple ammonium deep eutectic solvent, easily synthesized from choline chloride and tin chloride, is relatively inexpensive and recyclable, making it applicable for industrial applications.

Eutectic Salt Catalyzed Environmentally Benign and Highly Efficient Biginelli Reaction

PubMed Central

Azizi, Najmadin; Dezfuli, Sahar; Hahsemi, Mohmmad Mahmoodi

2012-01-01

A simple deep eutectic solvent based on tin (II) chloride was used as a dual catalyst and environmentally benign reaction medium for an efficient synthesis of 3,4-dihydropyrimidin-2(1H)-one derivatives, from aromatic and aliphatic aldehydes, 1,3-dicarbonyl compounds, and urea in good-to-excellent yields and short reaction time. This simple ammonium deep eutectic solvent, easily synthesized from choline chloride and tin chloride, is relatively inexpensive and recyclable, making it applicable for industrial applications. PMID:22649326

The time scale of quasifission process in reactions with heavy ions

NASA Astrophysics Data System (ADS)

Knyazheva, G. N.; Itkis, I. M.; Kozulin, E. M.

2014-05-01

The study of mass-energy distributions of binary fragments obtained in the reactions of 36S, 48Ca, 58Fe and 64Ni ions with the 232Th, 238U, 244Pu and 248Cm at energies below and above the Coulomb barrier is presented. These data have been measured by two time-of-flight CORSET spectrometer. The mass resolution of the spectrometer for these measurements was about 3u. It allows to investigate the features of mass distributions with good accuracy. The properties of mass and TKE of QF fragments in dependence on interaction energy have been investigated and compared with characteristics of the fusion-fission process. To describe the quasifission mass distribution the simple method has been proposed. This method is based on the driving potential of the system and time dependent mass drift. This procedure allows to estimate QF time scale from the measured mass distributions. It has been found that the QF time exponentially decreases when the reaction Coulomb factor Z1Z2 increases.

Shining X-rays on catalysts at work

NASA Astrophysics Data System (ADS)

Grunwaldt, J.-D.

2009-11-01

Structure-performance relationships gained by studying catalysts at work are considered the key to further development of catalysts underlined here by a brief overview on our research in this area. The partial oxidation of methane to hydrogen and carbon monoxide over Pt- and Rh-based catalysts and the total combustion of hydrocarbons demonstrate the importance of structural identification of catalysts in its working state and the measurement of the catalytic performance at the same time. Moreover, proper cell design is a key both here and in liquid phase reactions including preparation or high pressure reactions. In several cases structural changes during preparation, activation and reaction occur on a subminute scale or the catalyst structure varies inside a reactor as a result of temperature or concentration gradients. This, additionally, requires time and spatial resolution. Examples from time-resolved QEXAFS studies during the partial oxidation of methane over Pt- and Rh-based catalysts demonstrate some of the recent developments of the technique (use not only of Si(111) but also Si(311) crystals, angular encoder, full EXAFS spectra at subsecond recording time, and modulation excitation spectroscopy). In order to obtain spectroscopic information on the oxidation state inside a microreactor, scanning and full field X-ray microscopy with X-ray absorption spectroscopic contrast were achieved under reaction conditions. If a microbeam is applied, fast scanning techniques like QEXAFS are required. In this way, even X-ray absorption spectroscopic tomographic images of a slice of a microreactor were obtained. The studies were recently extended to spatiotemporal studies that give important insight into the dynamics of the catalyst structure in a spatial manner with subsecond time-resolution.

HRSSA - Efficient hybrid stochastic simulation for spatially homogeneous biochemical reaction networks

NASA Astrophysics Data System (ADS)

Marchetti, Luca; Priami, Corrado; Thanh, Vo Hong

2016-07-01

This paper introduces HRSSA (Hybrid Rejection-based Stochastic Simulation Algorithm), a new efficient hybrid stochastic simulation algorithm for spatially homogeneous biochemical reaction networks. HRSSA is built on top of RSSA, an exact stochastic simulation algorithm which relies on propensity bounds to select next reaction firings and to reduce the average number of reaction propensity updates needed during the simulation. HRSSA exploits the computational advantage of propensity bounds to manage time-varying transition propensities and to apply dynamic partitioning of reactions, which constitute the two most significant bottlenecks of hybrid simulation. A comprehensive set of simulation benchmarks is provided for evaluating performance and accuracy of HRSSA against other state of the art algorithms.

Crystallization stabilization mechanism of yttria-doped zirconia by hydrothermal treatment of mechanical mixtures of zirconia xerogel and crystalline yttria

NASA Astrophysics Data System (ADS)

Dell'Agli, G.; Mascolo, G.; Mascolo, M. C.; Pagliuca, C.

2005-06-01

Mechanical mixtures of zirconia xerogel and crystalline Y 2O 3 were hydrothermally treated by microwave and traditional route, respectively. Some mixtures were used either as powders form or as cylindrical compacts isostatically pressed at 150 MPa. The microwave-hydrothermal treatments were performed at 110, 150 and 200 °C for reaction times up to 2 h, whereas the traditional hydrothermal treatments were performed at 110 °C at increasing reaction times up to 7 days. All the treatments were performed in the presence of diluted (0.2 M) or concentrated (2.0 M) solution of (K 2CO 3+KOH) mineralizer. The crystallization-stabilization mechanism of synthesized Y-based zirconia powders and the reaction times for the full crystallization at the low temperature of hydrothermal treatments are discussed.

Rapid Catalyst Screening by a Continuous-Flow Microreactor Interfaced with Ultra High Pressure Liquid Chromatography

PubMed Central

Fang, Hui; Xiao, Qing; Wu, Fanghui; Floreancig, Paul E.; Weber, Stephen G.

2010-01-01

A high-throughput screening system for homogeneous catalyst discovery has been developed by integrating a continuous-flow capillary-based microreactor with ultra-high pressure liquid chromatography (UHPLC) for fast online analysis. Reactions are conducted in distinct and stable zones in a flow stream that allows for time and temperature regulation. UHPLC detection at high temperature allows high throughput online determination of substrate, product, and byproduct concentrations. We evaluated the efficacies of a series of soluble acid catalysts for an intramolecular Friedel-Crafts addition into an acyliminium ion intermediate within one day and with minimal material investment. The effects of catalyst loading, reaction time, and reaction temperature were also screened. This system exhibited high reproducibility for high-throughput catalyst screening and allowed several acid catalysts for the reaction to be identified. Major side products from the reactions were determined through off-line mass spectrometric detection. Er(OTf)3, the catalyst that showed optimal efficiency in the screening, was shown to be effective at promoting the cyclization reaction on a preparative scale. PMID:20666502

Phenol hydroxylation on Al-Fe modified-bentonite: Effect of Fe loading, temperature and reaction time

NASA Astrophysics Data System (ADS)

Widi, R. K.; Budhyantoro, A.; Christianto, A.

2017-11-01

The present work reflects the study of the phenol hydroxylation reactions to synthesize hydroquinone and catechol on Al-Fe modified-bentonite. This study started with synthesizes the catalyst material based on the modified bentonite. Natural bentonite from Pacitan, Indonesia was intercalated with Cetyl-TetramethylammoniumBromida (CTMA-Br) followed by pillarization using Alumina. The pillared bentonite was then impregnated with Fe solution (0.01 M, 0.05 M, and 0.1 M). The solid material obtained was calcined at 723 K for 4 hours. All the materials were characterized using BET N2 adsorption. Their catalytic activity and selectivity were studied for phenol hydroxylation using H2O2 (30%). The reaction conditions of this reaction were as follows: ratio of phenol/H2O2 = 1:1 (molar ratio), concentration of phenol = 1 M and ratio of catalyst/phenol was 1:10. Reaction temperatures were varied at 333, 343 and 353 K. The reaction time was also varied at 3, 4 and 5 hours. The result shows that the materials have potential catalyst activity.

Hydrolysis optimization and characterization study of preparing fatty acids from Jatropha curcas seed oil.

PubMed

Salimon, Jumat; Abdullah, Bashar Mudhaffar; Salih, Nadia

2011-11-01

Fatty acids (FAs) are important as raw materials for the biotechnology industry. Existing methods of FAs production are based on chemical methods. In this study potassium hydroxide (KOH)-catalyzed reactions were utilized to hydrolysis Jatropha curcas seed oil. The parameters effect of ethanolic KOH concentration, reaction temperature, and reaction time to free fatty acid (FFA%) were investigated using D-Optimal Design. Characterization of the product has been studied using Fourier transforms infrared spectroscopy (FTIR), gas chromatography (GC) and high performance liquid chromatography (HPLC). The optimum conditions for maximum FFA% were achieved at 1.75M of ethanolic KOH concentration, 65°C of reaction temperature and 2.0 h of reaction time. This study showed that ethanolic KOH concentration was significant variable for J. curcas seed oil hydrolysis. In a 18-point experimental design, FFA% of hydrolyzed J. curcas seed oil can be raised from 1.89% to 102.2%, which proved by FTIR and HPLC.

Development of an on-site rapid real-time polymerase chain reaction system and the characterization of suitable DNA polymerases for TaqMan probe technology.

PubMed

Furutani, Shunsuke; Naruishi, Nahoko; Hagihara, Yoshihisa; Nagai, Hidenori

2016-08-01

On-site quantitative analyses of microorganisms (including viruses) by the polymerase chain reaction (PCR) system are significantly influencing medical and biological research. We have developed a remarkably rapid and portable real-time PCR system that is based on microfluidic approaches. Real-time PCR using TaqMan probes consists of a complex reaction. Therefore, in a rapid real-time PCR, the optimum DNA polymerase must be estimated by using actual real-time PCR conditions. In this study, we compared the performance of three DNA polymerases in actual PCR conditions using our rapid real-time PCR system. Although KAPA2G Fast HS DNA Polymerase has the highest enzymatic activity among them, SpeedSTAR HS DNA Polymerase exhibited better performance to rapidly increase the fluorescence signal in an actual real-time PCR using TaqMan probes. Furthermore, we achieved rapid detection of Escherichia coli in 7 min by using SpeedSTAR HS DNA Polymerase with the same sensitivity as that of a conventional thermal cycler.

A theoretical study on tunneling based biosensor having a redox-active monolayer using physics based simulation

NASA Astrophysics Data System (ADS)

Kim, Kyoung Yeon; Lee, Won Cheol; Yun, Jun Yeon; Lee, Youngeun; Choi, Seoungwook; Jin, Seonghoon; Park, Young June

2018-01-01

We developed a numerical simulator to model the operation of a tunneling based biosensor which has a redox-active monolayer. The simulator takes a realistic device structure as a simulation domain, and it employs the drift-diffusion equation for ion transport, the non-equilibrium Green's function formalism for electron tunneling, and the Ramo-Shockley theorem for accurate calculation of non-faradaic current. We also accounted for the buffer reaction and the immobilized peptide layer. For efficient transient simulation, the implicit time integration scheme is employed where the solution at each time step is obtained from the coupled Newton-Raphson method. As an application, we studied the operation of a recently fabricated reference-electrode free biosensor in various bias conditions and confirmed the effect of buffer reaction and the current flowing mechanism. Using the simulator, we also found a strategy to maximize the sensitivity of the tunneling based sensor.

Autonomous Vehicles: Disengagements, Accidents and Reaction Times.

PubMed

Dixit, Vinayak V; Chand, Sai; Nair, Divya J

2016-01-01

Autonomous vehicles are being viewed with scepticism in their ability to improve safety and the driving experience. A critical issue with automated driving at this stage of its development is that it is not yet reliable and safe. When automated driving fails, or is limited, the autonomous mode disengages and the drivers are expected to resume manual driving. For this transition to occur safely, it is imperative that drivers react in an appropriate and timely manner. Recent data released from the California trials provide compelling insights into the current factors influencing disengagements of autonomous mode. Here we show that the number of accidents observed has a significantly high correlation with the autonomous miles travelled. The reaction times to take control of the vehicle in the event of a disengagement was found to have a stable distribution across different companies at 0.83 seconds on average. However, there were differences observed in reaction times based on the type of disengagements, type of roadway and autonomous miles travelled. Lack of trust caused by the exposure to automated disengagements was found to increase the likelihood to take control of the vehicle manually. Further, with increased vehicle miles travelled the reaction times were found to increase, which suggests an increased level of trust with more vehicle miles travelled. We believe that this research would provide insurers, planners, traffic management officials and engineers fundamental insights into trust and reaction times that would help them design and engineer their systems.

Autonomous Vehicles: Disengagements, Accidents and Reaction Times

PubMed Central

Dixit, Vinayak V.; Chand, Sai; Nair, Divya J.

2016-01-01

Autonomous vehicles are being viewed with scepticism in their ability to improve safety and the driving experience. A critical issue with automated driving at this stage of its development is that it is not yet reliable and safe. When automated driving fails, or is limited, the autonomous mode disengages and the drivers are expected to resume manual driving. For this transition to occur safely, it is imperative that drivers react in an appropriate and timely manner. Recent data released from the California trials provide compelling insights into the current factors influencing disengagements of autonomous mode. Here we show that the number of accidents observed has a significantly high correlation with the autonomous miles travelled. The reaction times to take control of the vehicle in the event of a disengagement was found to have a stable distribution across different companies at 0.83 seconds on average. However, there were differences observed in reaction times based on the type of disengagements, type of roadway and autonomous miles travelled. Lack of trust caused by the exposure to automated disengagements was found to increase the likelihood to take control of the vehicle manually. Further, with increased vehicle miles travelled the reaction times were found to increase, which suggests an increased level of trust with more vehicle miles travelled. We believe that this research would provide insurers, planners, traffic management officials and engineers fundamental insights into trust and reaction times that would help them design and engineer their systems. PMID:27997566

Assessment of pedophilic sexual interest with an attentional choice reaction time task.

PubMed

Mokros, Andreas; Dombert, Beate; Osterheider, Michael; Zappalà, Angelo; Santtila, Pekka

2010-10-01

Choice-reaction time (CRT) is an experimental information-processing paradigm. Based on an interference effect in visual attention, the CRT method has been shown to be suitable for measuring sexual orientation in men and women. The present study assessed the potential of the CRT to identify deviant (i.e., pedophilic) sexual interest. Participants were patients from forensic-psychiatric hospitals: 21 child molesters and 21 non-sex offenders. The dependent variable was reaction time in an ostensible seek-and-locate task (i.e., identifying the position of a dot superimposed on a picture of a person). There was an interaction effect between stimulus age category and participant group status: Child molesters took longer to respond to pictures of children relative to pictures of adults. Non-sex offenders showed an opposite pattern (i.e., longer reaction times with pictures of adults than with pictures of children). In addition, the data supported the notion of sexual content induced delay: Subjects took longer for the task with nude stimuli than with clothed ones. A subtractive preference index, derived from the reaction times for child and adult stimulus material, allowed distinguishing participants from both groups almost perfectly (ROC-AUC = .998). We conclude that a match of sexual interest with properties of visual stimuli led to a cognitive interference effect: Attentional resources were drawn from the ostensible task of locating the dot towards exploring the picture. This opens up the possibility of using this interference effect (i.e., the delay of response times) for diagnostic purposes.

Reaction front dynamics under shear flow for arbitrary Damköhler numbers

NASA Astrophysics Data System (ADS)

Bandopadhyay, Aditya; Méheust, Yves; Le Borgne, Tanguy

2016-04-01

Reaction fronts where two reactive fluids displace one another play an important role in a range of applications, including contaminant plume transport and reaction, soil and aquifer remediation, CO2 sequestration, geothermal dipoles and the development of hotspots of reaction in mixing zones. The background flow induces enhanced mixing, and therefore reaction, through interfacial shear. Hence the coupling of fluid flow with chemical reactions is pivotal in understanding and quantifying effective reaction kinetics in reaction fronts. While this problem has been addressed in the limit of fast reactions (e.g. de Simoni 2005, Le Borgne 2014), in natural systems reactions can span a large range of Damköhler numbers since their characteristic reaction times vary over a large range of typical values. Here the coupling of shear flow and reversible chemical reactions is studied for a reaction front with initially separated reactants at arbitrary Damköhler numbers. Approximate analytical expressions for the global production rate are derived based on a reactive lamella approach. We observe three distinct regimes, each of them characterized by different scalings of the global production rate and width of the reactive zone. We describe the dependency of these scalings and the associated characteristic transition times as a function of Damköhler and Péclet numbers. These results are validated against 2D numerical simulations. The study is expected to shed light on the inherently complex cases of reactive mixing with varying reaction rates under the influence of an imposed flow. de Simoni et al. (2005) Water Resour. Res., 41, W11410 Le Borgne et al. (2014) GRL, 41(22), 7898

Highly efficient preparation of sphingoid bases from glucosylceramides by chemoenzymatic method[S

PubMed Central

Gowda, Siddabasave Gowda B.; Usuki, Seigo; Hammam, Mostafa A. S.; Murai, Yuta; Igarashi, Yasuyuki; Monde, Kenji

2016-01-01

Sphingoid base derivatives have attracted increasing attention as promising chemotherapeutic candidates against lifestyle diseases such as diabetes and cancer. Natural sphingoid bases can be a potential resource instead of those derived by time-consuming total organic synthesis. In particular, glucosylceramides (GlcCers) in food plants are enriched sources of sphingoid bases, differing from those of animals. Several chemical methodologies to transform GlcCers to sphingoid bases have already investigated; however, these conventional methods using acid or alkaline hydrolysis are not efficient due to poor reaction yield, producing complex by-products and resulting in separation problems. In this study, an extremely efficient and practical chemoenzymatic transformation method has been developed using microwave-enhanced butanolysis of GlcCers and a large amount of readily available almond β-glucosidase for its deglycosylation reaction of lysoGlcCers. The method is superior to conventional acid/base hydrolysis methods in its rapidity and its reaction cleanness (no isomerization, no rearrangement) with excellent overall yield. PMID:26667669

An optics-based variable-temperature assay system for characterizing thermodynamics of biomolecular reactions on solid support

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

Fei, Yiyan; Landry, James P.; Zhu, X. D., E-mail: xdzhu@physics.ucdavis.edu

A biological state is equilibrium of multiple concurrent biomolecular reactions. The relative importance of these reactions depends on physiological temperature typically between 10 °C and 50 °C. Experimentally the temperature dependence of binding reaction constants reveals thermodynamics and thus details of these biomolecular processes. We developed a variable-temperature opto-fluidic system for real-time measurement of multiple (400–10 000) biomolecular binding reactions on solid supports from 10 °C to 60 °C within ±0.1 °C. We illustrate the performance of this system with investigation of binding reactions of plant lectins (carbohydrate-binding proteins) with 24 synthetic glycans (i.e., carbohydrates). We found that the lectin-glycan reactions in general can be enthalpy-driven,more » entropy-driven, or both, and water molecules play critical roles in the thermodynamics of these reactions.« less

Position-sensitive coincidence detection of nuclear reaction products at the Prague Van-de-Graaff accelerator

NASA Astrophysics Data System (ADS)

Granja, Carlos; Kraus, Vaclav; Pugatch, Valery; Kohout, Zdenek

2017-06-01

In low-energy nuclear reactions of astrophysical interest or fusion studies the spatial- and time-correlated detection of two and more reaction products can be a valuable tool in studies of reaction mechanisms, resolving reaction channels and measuring angular distributions of reaction products. For this purpose we constructed a configurable array of position-sensitive detectors based on the hybrid semiconductor pixel detector Timepix. Additional analog-signal electronics provide self-trigger together with extended multi-device control and synchronized readout electronics by a customized control and coincidence unit. The instrumentation, developed and used for detection of fission fragments in spontaneous and neutron induced fission as well as in charged particle detection in neutron induced reactions, is being implemented for low-energy light-ion induced nuclear reactions. Application and demonstration of the technique with two Timepix detectors on p+p elastic scattering at the Van-de-Graaff (VdG) accelerator in Prague is given.

An optics-based variable-temperature assay system for characterizing thermodynamics of biomolecular reactions on solid support

NASA Astrophysics Data System (ADS)

Fei, Yiyan; Landry, James P.; Li, Yanhong; Yu, Hai; Lau, Kam; Huang, Shengshu; Chokhawala, Harshal A.; Chen, Xi; Zhu, X. D.

2013-11-01

A biological state is equilibrium of multiple concurrent biomolecular reactions. The relative importance of these reactions depends on physiological temperature typically between 10 °C and 50 °C. Experimentally the temperature dependence of binding reaction constants reveals thermodynamics and thus details of these biomolecular processes. We developed a variable-temperature opto-fluidic system for real-time measurement of multiple (400-10 000) biomolecular binding reactions on solid supports from 10 °C to 60 °C within ±0.1 °C. We illustrate the performance of this system with investigation of binding reactions of plant lectins (carbohydrate-binding proteins) with 24 synthetic glycans (i.e., carbohydrates). We found that the lectin-glycan reactions in general can be enthalpy-driven, entropy-driven, or both, and water molecules play critical roles in the thermodynamics of these reactions.

Networks of connected Pt nanoparticles supported on carbon nanotubes as superior catalysts for methanol electrooxidation

NASA Astrophysics Data System (ADS)

Huang, Meihua; Zhang, Jianshuo; Wu, Chuxin; Guan, Lunhui

2017-02-01

The high cost and short lifetime of the Pt-based anode catalyst for methanol oxidation reaction (MOR) hamper the widespread commercialization of direct methanol fuel cell (DMFC). Therefore, improving the activity of Pt-based catalysts is necessary for their practical application. For the first time, we prepared networks of connected Pt nanoparticles supported on multi-walled carbon nanotubes with loading ratio as high as 91 wt% (Pt/MWCNTs). Thanks for the unique connected structure, the Pt mass activity of Pt/MWCNTs for methanol oxidation reaction is 4.4 times as active as that of the commercial Pt/C (20 wt%). When carbon support is considered, the total mass activity of Pt/MWCNTs is 20 times as active as that of the commercial Pt/C. The durability and anti-poisoning ability are also improved greatly.

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

Mondy, Lisa Ann; Rao, Rekha Ranjana; Shelden, Bion

We are developing computational models to elucidate the expansion and dynamic filling process of a polyurethane foam, PMDI. The polyurethane of interest is chemically blown, where carbon dioxide is produced via the reaction of water, the blowing agent, and isocyanate. The isocyanate also reacts with polyol in a competing reaction, which produces the polymer. Here we detail the experiments needed to populate a processing model and provide parameters for the model based on these experiments. The model entails solving the conservation equations, including the equations of motion, an energy balance, and two rate equations for the polymerization and foaming reactions,more » following a simplified mathematical formalism that decouples these two reactions. Parameters for the polymerization kinetics model are reported based on infrared spectrophotometry. Parameters describing the gas generating reaction are reported based on measurements of volume, temperature and pressure evolution with time. A foam rheology model is proposed and parameters determined through steady-shear and oscillatory tests. Heat of reaction and heat capacity are determined through differential scanning calorimetry. Thermal conductivity of the foam as a function of density is measured using a transient method based on the theory of the transient plane source technique. Finally, density variations of the resulting solid foam in several simple geometries are directly measured by sectioning and sampling mass, as well as through x-ray computed tomography. These density measurements will be useful for model validation once the complete model is implemented in an engineering code.« less

The Simplest Chronoscope V: A Theory of Dual Primary and Secondary Reaction Time Systems.

PubMed

Montare, Alberto

2016-12-01

Extending work by Montare, visual simple reaction time, choice reaction time, discriminative reaction time, and overall reaction time scores obtained from college students by the simplest chronoscope (a falling meterstick) method were significantly faster as well as significantly less variable than scores of the same individuals from electromechanical reaction timers (machine method). Results supported the existence of dual reaction time systems: an ancient primary reaction time system theoretically activating the V5 parietal area of the dorsal visual stream that evolved to process significantly faster sensory-motor reactions to sudden stimulations arising from environmental objects in motion, and a secondary reaction time system theoretically activating the V4 temporal area of the ventral visual stream that subsequently evolved to process significantly slower sensory-perceptual-motor reactions to sudden stimulations arising from motionless colored objects. © The Author(s) 2016.

Typewriting rate as a function of reaction time.

PubMed

Hayes, V; Wilson, G D; Schafer, R L

1977-12-01

This study was designed to determine the relationship between reaction time and typewriting rate. Subjects were 24 typists ranging in age from 19 to 39 yr. Reaction times (.001 sec) to a light were recorded for each finger and to each alphabetic character and three punctuation marks. Analysis of variance yielded significant differences in reaction time among subjects and fingers. Correlation between typewriting rate and average reaction time to the alphabetic characters and three punctuation marks was --.75. Correlation between typewriting rate and the difference between the reaction time of the hands was --.42. Factors influencing typewriting rate may include reaction time of the fingers, difference between the reaction time of the hands, and reaction time to individual keys on the typewriter. Implications exist for instructional methodology and further research.

Scavenging and recombination kinetics in a radiation spur: The successive ordered scavenging events

NASA Astrophysics Data System (ADS)

Al-Samra, Eyad H.; Green, Nicholas J. B.

2018-03-01

This study describes stochastic models to investigate the successive ordered scavenging events in a spur of four radicals, a model system based on a radiation spur. Three simulation models have been developed to obtain the probabilities of the ordered scavenging events: (i) a Monte Carlo random flight (RF) model, (ii) hybrid simulations in which the reaction rate coefficient is used to generate scavenging times for the radicals and (iii) the independent reaction times (IRT) method. The results of these simulations are found to be in agreement with one another. In addition, a detailed master equation treatment is also presented, and used to extract simulated rate coefficients of the ordered scavenging reactions from the RF simulations. These rate coefficients are transient, the rate coefficients obtained for subsequent reactions are effectively equal, and in reasonable agreement with the simple correction for competition effects that has recently been proposed.

Estimating the executive demands of a one-back choice reaction time task by means of the selective interference paradigm.

PubMed

Szmalec, Arnaud; Vandierendonck, André

2007-08-01

The present study proposes a new executive task, the one-back choice reaction time (RT) task, and implements the selective interference paradigm to estimate the executive demands of the processing components involved in this task. Based on the similarities between a one-back choice RT task and the n-back updating task, it was hypothesized that one-back delaying of a choice reaction involves executive control. In three experiments, framed within Baddeley's (1986) working-memory model, a one-back choice RT task, a choice RT task, articulatory suppression, and matrix tapping were performed concurrently with primary tasks involving verbal, visuospatial, and executive processing. The results demonstrate that one-back delaying of a choice reaction interferes with tasks requiring executive control, while the potential interference at the level of the verbal or visuospatial working memory slave systems remains minimal.

Dual phase multiplex polymerase chain reaction

DOEpatents

Pemov, Alexander [Charlottesville, VA; Bavykin, Sergei [Darien, IL

2008-10-07

Highly specific and sensitive methods were developed for multiplex amplification of nucleic acids on supports such as microarrays. Based on a specific primer design, methods include five types of amplification that proceed in a reaction chamber simultaneously. These relate to four types of multiplex amplification of a target DNA on a solid support, directed by forward and reverse complex primers immobilized to the support and a fifth type--pseudo-monoplex polymerase chain reaction (PCR) of multiple targets in solution, directed by a single pair of unbound universal primers. The addition of the universal primers in the reaction mixture increases the yield over the traditional "bridge" amplification on a solid support by approximately ten times. Methods that provide multitarget amplification and detection of as little as 0.45-4.5.times.10.sup.-12 g (equivalent to 10.sup.2-10.sup.3 genomes) of a bacterial genomic DNA are disclosed.

Process characteristics for microwave assisted hydrothermal carbonization of cellulose.

PubMed

Zhang, Junting; An, Ying; Borrion, Aiduan; He, Wenzhi; Wang, Nan; Chen, Yirong; Li, Guangming

2018-07-01

The process characteristics of microwave assisted hydrothermal carbonization of cellulose was investigated and a first order kinetics model based on carbon concentration was developed. Chemical properties analysis showed that comparing to conventional hydrothermal carbonization, hydrochar with comparable energy properties can be obtained with 5-10 times decrease in reaction time with assistance of microwave heating. Results from kinetics study was in great agreement with experimental analysis, that they both illustrated the predominant mechanism of the reaction depend on variations in the reaction rates of two co-existent pathways. Particularly, the pyrolysis-like intramolecular dehydration reaction was proved to be the predominant mechanism for hydrochar generation under high temperatures. Finally, the enhancement effects of microwave heating were reflected under both soluble and solid pathways in this research, suggesting microwave-assisted hydrothermal carbonization as a more attracting method for carbon-enriched hydrochar recovery. Copyright © 2018 Elsevier Ltd. All rights reserved.

pH Wave-Front Propagation in the Urea-Urease Reaction

PubMed Central

Wrobel, Magdalena M.; Bánsági, Tamás; Scott, Stephen K.; Taylor, Annette F.; Bounds, Chris O.; Carranza, Arturo; Pojman, John A.

2012-01-01

The urease-catalyzed hydrolysis of urea displays feedback that results in a switch from acid (pH ∼3) to base (pH ∼9) after a controllable period of time (from 10 to >5000 s). Here we show that the spatially distributed reaction can support pH wave fronts propagating with a speed of the order of 0.1−1 mm min−1. The experimental results were reproduced qualitatively in reaction-diffusion simulations including a Michaelis-Menten expression for the urease reaction with a bell-shaped rate-pH dependence. However, this model fails to predict that at lower enzyme concentrations, the unstirred reaction does not always support fronts when the well-stirred reaction still rapidly switches to high pH. PMID:22947878

Cycom 977-2 Composite Material: Impact Test Results

NASA Technical Reports Server (NTRS)

Engel, Carl D.; Herald, Stephen; Watkins, Casey

2005-01-01

The reaction frequency data from 13A testing by MSFC and WSTF appear well behaved for the sample number used by each and exhibit the same type of energy level dependency. The reaction frequency shift in energy level is unexplained at this time. All the 13A data suggest that only a small amount of material is consumed when reactions take place. At ambient pressure, most of not all reactions are quenched as indicated by the small mass loss. As test pressure is increased in LOX using 13B results. Cycom does not support initiation of reactions or propagations of reactions in GOX at 100 psis based on tests at MSFC and WSTF at 72 ft-lb impact energy. No batch effect was identified in LOX or GOX.

Development of melting temperature-based SYBR Green I polymerase chain reaction methods for multiplex genetically modified organism detection.

PubMed

Hernández, Marta; Rodríguez-Lázaro, David; Esteve, Teresa; Prat, Salomé; Pla, Maria

2003-12-15

Commercialization of several genetically modified crops has been approved worldwide to date. Uniplex polymerase chain reaction (PCR)-based methods to identify these different insertion events have been developed, but their use in the analysis of all commercially available genetically modified organisms (GMOs) is becoming progressively insufficient. These methods require a large number of assays to detect all possible GMOs present in the sample and thereby the development of multiplex PCR systems using combined probes and primers targeted to sequences specific to various GMOs is needed for detection of this increasing number of GMOs. Here we report on the development of a multiplex real-time PCR suitable for multiple GMO identification, based on the intercalating dye SYBR Green I and the analysis of the melting curves of the amplified products. Using this method, different amplification products specific for Maximizer 176, Bt11, MON810, and GA21 maize and for GTS 40-3-2 soybean were obtained and identified by their specific Tm. We have combined amplification of these products in a number of multiplex reactions and show the suitability of the methods for identification of GMOs with a sensitivity of 0.1% in duplex reactions. The described methods offer an economic and simple alternative to real-time PCR systems based on sequence-specific probes (i.e., TaqMan chemistry). These methods can be used as selection tests and further optimized for uniplex GMO quantification.

Hierarchically Nanostructured Transition Metal Oxides for Lithium‐Ion Batteries

PubMed Central

Zheng, Mingbo; Tang, Hao; Li, Lulu; Hu, Qin; Zhang, Li; Xue, Huaiguo

2018-01-01

Abstract Lithium‐ion batteries (LIBs) have been widely used in the field of portable electric devices because of their high energy density and long cycling life. To further improve the performance of LIBs, it is of great importance to develop new electrode materials. Various transition metal oxides (TMOs) have been extensively investigated as electrode materials for LIBs. According to the reaction mechanism, there are mainly two kinds of TMOs, one is based on conversion reaction and the other is based on intercalation/deintercalation reaction. Recently, hierarchically nanostructured TMOs have become a hot research area in the field of LIBs. Hierarchical architecture can provide numerous accessible electroactive sites for redox reactions, shorten the diffusion distance of Li‐ion during the reaction, and accommodate volume expansion during cycling. With rapid research progress in this field, a timely account of this advanced technology is highly necessary. Here, the research progress on the synthesis methods, morphological characteristics, and electrochemical performances of hierarchically nanostructured TMOs for LIBs is summarized and discussed. Some relevant prospects are also proposed. PMID:29593962

An experimental and theoretical study of reaction mechanisms between nitriles and hydroxylamine.

PubMed

Vörös, Attila; Mucsi, Zoltán; Baán, Zoltán; Timári, Géza; Hermecz, István; Mizsey, Péter; Finta, Zoltán

2014-10-28

The industrially relevant reaction between nitriles and hydroxylamine yielding amidoximes was studied in different molecular solvents and in ionic liquids. In industry, this procedure is carried out on the ton scale in alcohol solutions and the above transformation produces a significant amount of unexpected amide by-product, depending on the nature of the nitrile, which can cause further analytical and purification issues. Although there were earlier attempts to propose mechanisms for this transformation, the real reaction pathway is still under discussion. A new detailed reaction mechanistic explanation, based on theoretical and experimental proof, is given to augment the former mechanisms, which allowed us to find a more efficient, side-product free procedure. Interpreting the theoretical results obtained, it was shown that the application of specific imidazolium, phosphonium and quaternary ammonium based ionic liquids could decrease simultaneously the reaction time while eliminating the amide side-product, leading to the targeted product selectively. This robust and economic procedure now affords a fast, selective amide free synthesis of amidoximes.

Hierarchically Nanostructured Transition Metal Oxides for Lithium-Ion Batteries.

PubMed

Zheng, Mingbo; Tang, Hao; Li, Lulu; Hu, Qin; Zhang, Li; Xue, Huaiguo; Pang, Huan

2018-03-01

Lithium-ion batteries (LIBs) have been widely used in the field of portable electric devices because of their high energy density and long cycling life. To further improve the performance of LIBs, it is of great importance to develop new electrode materials. Various transition metal oxides (TMOs) have been extensively investigated as electrode materials for LIBs. According to the reaction mechanism, there are mainly two kinds of TMOs, one is based on conversion reaction and the other is based on intercalation/deintercalation reaction. Recently, hierarchically nanostructured TMOs have become a hot research area in the field of LIBs. Hierarchical architecture can provide numerous accessible electroactive sites for redox reactions, shorten the diffusion distance of Li-ion during the reaction, and accommodate volume expansion during cycling. With rapid research progress in this field, a timely account of this advanced technology is highly necessary. Here, the research progress on the synthesis methods, morphological characteristics, and electrochemical performances of hierarchically nanostructured TMOs for LIBs is summarized and discussed. Some relevant prospects are also proposed.

Real-time monitoring of disintegration activity of catalytic core domain of HIV-1 integrase using molecular beacon.

PubMed

Zhang, Da-wei; Zhao, Ming-ming; He, Hong-qiu; Guo, Shun-xing

2013-09-15

HIV-1 integrase, an essential enzyme for retroviral replication, is a validated target for anti-HIV therapy development. The catalytic core domain of integrase (IN-CCD) is capable of catalyzing disintegration reaction. In this work, a hairpin-shaped disintegration substrate was designed and validated by enzyme-linked immunosorbent assay; a molecular beacon-based assay was developed for disintegration reaction of IN-CCD. Results showed that the disintegration substrate could be recognized and catalyzed by IN-CCD, and the disintegration reaction can be monitored according to the increase of fluorescent signal. The assay can be applied to real-time detection of disintegration with advantages of simplicity, high sensitivity, and excellent specificity. Copyright © 2013 Elsevier Inc. All rights reserved.

Multiplex Detection of Aspergillus Species.

PubMed

Martínez-Culebras, Pedro; Selma, María Victoria; Aznar, Rosa

2017-01-01

Multiplex real-time polymerase chain reaction (PCR) provides a fast and accurate DNA-based tool for the simultaneous amplification of more than one target sequence in a single reaction. Here a duplex real-time PCR assay is described for the simultaneous detection of Aspergillus carbonarius and members of the Aspergillus niger aggregate, which are the main responsible species for ochratoxin A (OTA) contamination in grapes. This single tube reaction targets the beta-ketosynthase and the acyl transferase domains of the polyketide synthase of A. carbonarius and the A. niger aggregate, respectively.Besides, a rapid and efficient fungi DNA extraction procedure is described suitable to be applied in wine grapes. It includes a pulsifier equipment to remove conidia from grapes which prevents releasing of PCR inhibitors.

Quantitative real-time imaging of glutathione

USDA-ARS?s Scientific Manuscript database

Glutathione plays many important roles in biological processes; however, the dynamic changes of glutathione concentrations in living cells remain largely unknown. Here, we report a reversible reaction-based fluorescent probe—designated as RealThiol (RT)—that can quantitatively monitor the real-time ...

Making it stick: convection, reaction and diffusion in surface-based biosensors.

PubMed

Squires, Todd M; Messinger, Robert J; Manalis, Scott R

2008-04-01

The past decade has seen researchers develop and apply novel technologies for biomolecular detection, at times approaching hard limits imposed by physics and chemistry. In nearly all sensors, the transport of target molecules to the sensor can play as critical a role as the chemical reaction itself in governing binding kinetics, and ultimately performance. Yet rarely does an analysis of the interplay between diffusion, convection and reaction motivate experimental design or interpretation. Here we develop a physically intuitive and practical understanding of analyte transport for researchers who develop and employ biosensors based on surface capture. We explore the qualitatively distinct behaviors that result, develop rules of thumb to quickly determine how a given system will behave, and derive order-of-magnitude estimates for fundamental quantities of interest, such as fluxes, collection rates and equilibration times. We pay particular attention to collection limits for micro- and nanoscale sensors, and highlight unexplained discrepancies between reported values and theoretical limits.

Lab-on-a-chip with beta-poly(vinylidene fluoride) based acoustic microagitation.

PubMed

Cardoso, V F; Catarino, S O; Serrado Nunes, J; Rebouta, L; Rocha, J G; Lanceros-Méndez, S; Minas, G

2010-05-01

This paper reports a fully integrated disposable lab-on-a-chip with acoustic microagitation based on a piezoelectric ss-poly(vinylidene fluoride) (ss-PVDF) polymer. The device can be used for the measurement, by optical absorption spectroscopy, of biochemical parameters in physiological fluids. It comprises two dies: the fluidic die that contains the reaction chambers fabricated in SU-8 and the ss-PVDF polymer deposited underneath them; and the detection die that contains the photodetectors, its readout electronics, and the piezoelectric actuation electronics, all fabricated in a CMOS microelectronic process. The microagitation technique improves mixing and shortens reaction time. Further, it generates heating, which also improves the reaction time of the fluids. In this paper, the efficiency of the microagitation system is evaluated as a function of the amplitude and the frequency of the signal actuation. The relative contribution of the generated heating is also discussed. The system is tested for the measurement of the uric acid concentration in urine.

The Potential of Biodiesel Production derived from Fish Waste

NASA Astrophysics Data System (ADS)

Farzana Samat, Amira; Amirah Safiah Muhamad, Nor; Rasib, Nur Aziera Abd; Hassan, Siti Aminah Mohd; Sohaimi, Khairunissa Syairah Ahmad; Izzati Iberahim, Nur

2018-03-01

Petroleum based diesel is one of the largest greenhouse emitters in the worlds based on its contribution to more likely of all carbon, methane and other greenhouse emissions. Besides, the depletion of fossil fuel that indirectly increased its price has force the global oil industry not to be so dependent on the fossil fuel but instead start focusing on alternative sources. Biodiesel is recognized as a clean alternative fuel or as a fuel additive to reduce pollutant from combustion equipment. In this study, the discarded parts of mixed marine fish species were used as the raw material to produce biodiesel. Marine fish oil was extracted from the discarded part of fish and if refined through a series of pretreatment process. The refined marine fish oil undergoes esterification process to reduce the amount of free fatty acid. The oil was then transesterified with methanol and sodium hydroxide as an alkaline catalyst that will speed up the conversion of oil to methyl ester. The three process parameters considered for this study were reaction time, reaction temperature and methanol to oil molar ratio. Biodiesel obtained was then analyzed using gas chromatography (GC). Statistical analyses were performed using SPSS software. The data obtained was analyzed by using one way analysis of variance (ANOVA) repeated measure. The results obtained showed that the conversion of FAME yield is the highest at reaction time 180 minutes, reaction temperature 60°C and methanol to oil molar ratio at 15:1 with FAME yield 80.16%, 80.03% and 80.39%. Thus, it can be concluded that the conversion of biodiesel increased as the reaction time, temperature and

An accelerated algorithm for discrete stochastic simulation of reaction-diffusion systems using gradient-based diffusion and tau-leaping.

PubMed

Koh, Wonryull; Blackwell, Kim T

2011-04-21

Stochastic simulation of reaction-diffusion systems enables the investigation of stochastic events arising from the small numbers and heterogeneous distribution of molecular species in biological cells. Stochastic variations in intracellular microdomains and in diffusional gradients play a significant part in the spatiotemporal activity and behavior of cells. Although an exact stochastic simulation that simulates every individual reaction and diffusion event gives a most accurate trajectory of the system's state over time, it can be too slow for many practical applications. We present an accelerated algorithm for discrete stochastic simulation of reaction-diffusion systems designed to improve the speed of simulation by reducing the number of time-steps required to complete a simulation run. This method is unique in that it employs two strategies that have not been incorporated in existing spatial stochastic simulation algorithms. First, diffusive transfers between neighboring subvolumes are based on concentration gradients. This treatment necessitates sampling of only the net or observed diffusion events from higher to lower concentration gradients rather than sampling all diffusion events regardless of local concentration gradients. Second, we extend the non-negative Poisson tau-leaping method that was originally developed for speeding up nonspatial or homogeneous stochastic simulation algorithms. This method calculates each leap time in a unified step for both reaction and diffusion processes while satisfying the leap condition that the propensities do not change appreciably during the leap and ensuring that leaping does not cause molecular populations to become negative. Numerical results are presented that illustrate the improvement in simulation speed achieved by incorporating these two new strategies.

Transformation of amorphous TiO 2 to a hydronium oxofluorotitanate and applications as an HF sensor

DOE PAGES

Appelhans, Leah N.; Finnegan, Patrick S.; Massey, Lee T.; ...

2015-12-24

We examined amorphous titania thin films for use as the active material in a polarimetry based HF sensor. The amorphous titania films were found to be sensitive to vapor phase HF and the reaction product was identified as a hydronium oxofluorotitanate phase, which has previously only been synthesized in aqueous solution. The extent of reaction varied both with vapor phase HF concentration, relative humidity, and the exposure time. HF concentrations as low as 1 ppm could be detected for exposure times of 120 h.

Normobaric hypoxia overnight impairs cognitive reaction time.

PubMed

Pramsohler, Stephan; Wimmer, Stefan; Kopp, Martin; Gatterer, Hannes; Faulhaber, Martin; Burtscher, Martin; Netzer, Nikolaus Cristoph

2017-05-15

Impaired reaction time in patients suffering from hypoxia during sleep, caused by sleep breathing disorders, is a well-described phenomenon. High altitude sleep is known to induce periodic breathing with central apneas and oxygen desaturations, even in perfectly healthy subjects. However, deficits in reaction time in mountaineers or workers after just some nights of hypoxia exposure are not sufficiently explored. Therefore, we aimed to investigate the impact of sleep in a normobaric hypoxic environment on reaction time divided by its cognitive and motoric components. Eleven healthy non acclimatized students (5f, 6m, 21 ± 2.1 years) slept one night at a simulated altitude of 3500 m in a normobaric hypoxic room, followed by a night with polysomnography at simulated 5500 m. Preexisting sleep disorders were excluded via BERLIN questionnaire. All subjects performed a choice reaction test (SCHUHFRIED RT, S3) at 450 m and directly after the nights at simulated 3500 and 5500 m. We found a significant increase of cognitive reaction time with higher altitude (p = 0.026). No changes were detected in movement time (p = n.s.). Reaction time, the combined parameter of cognitive- and motoric reaction time, didn't change either (p = n.s.). Lower SpO 2 surprisingly correlated significantly with shorter cognitive reaction time (r = 0.78, p = 0.004). Sleep stage distribution and arousals at 5500 m didn't correlate with reaction time, cognitive reaction time or movement time. Sleep in hypoxia does not seem to affect reaction time to simple tasks. The component of cognitive reaction time is increasingly delayed whereas motoric reaction time seems not to be affected. Low SpO 2 and arousals are not related to increased cognitive reaction time therefore the causality remains unclear. The fact of increased cognitive reaction time after sleep in hypoxia, considering high altitude workers and mountaineering operations with overnight stays, should be further investigated.

Real-time PCR detection chemistry.

PubMed

Navarro, E; Serrano-Heras, G; Castaño, M J; Solera, J

2015-01-15

Real-time PCR is the method of choice in many laboratories for diagnostic and food applications. This technology merges the polymerase chain reaction chemistry with the use of fluorescent reporter molecules in order to monitor the production of amplification products during each cycle of the PCR reaction. Thus, the combination of excellent sensitivity and specificity, reproducible data, low contamination risk and reduced hand-on time, which make it a post-PCR analysis unnecessary, has made real-time PCR technology an appealing alternative to conventional PCR. The present paper attempts to provide a rigorous overview of fluorescent-based methods for nucleic acid analysis in real-time PCR described in the literature so far. Herein, different real-time PCR chemistries have been classified into two main groups; the first group comprises double-stranded DNA intercalating molecules, such as SYBR Green I and EvaGreen, whereas the second includes fluorophore-labeled oligonucleotides. The latter, in turn, has been divided into three subgroups according to the type of fluorescent molecules used in the PCR reaction: (i) primer-probes (Scorpions, Amplifluor, LUX, Cyclicons, Angler); (ii) probes; hydrolysis (TaqMan, MGB-TaqMan, Snake assay) and hybridization (Hybprobe or FRET, Molecular Beacons, HyBeacon, MGB-Pleiades, MGB-Eclipse, ResonSense, Yin-Yang or displacing); and (iii) analogues of nucleic acids (PNA, LNA, ZNA, non-natural bases: Plexor primer, Tiny-Molecular Beacon). In addition, structures, mechanisms of action, advantages and applications of such real-time PCR probes and analogues are depicted in this review. Copyright © 2014 Elsevier B.V. All rights reserved.

Principal Investigator in a Box Technical Description Document. 2.0

NASA Technical Reports Server (NTRS)

Groleau, Nick; Frainier, Richard

1994-01-01

This document provides a brief overview of the PI-in-a-Box system, which can be used for automatic real-time reaction to incoming data. We will therefore outline the current system's capabilities and limitations, and hint at how best to think about PI-in-a-Box as a tool for real-time analysis and reaction in section two, below. We also believe that the solution to many commercial real-time process problems requires data acquisition and analysis combined with rule-based reasoning and/or an intuitive user interface. We will develop the technology reuse potential in section three. Currently, the system runs only on Apple Computer's Macintosh series.

Development of Customized [18F]Fluoride Elution Techniques for the Enhancement of Copper-Mediated Late-Stage Radiofluorination

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

Mossine, Andrew V.; Brooks, Allen F.; Ichiishi, Naoko

In a relatively short period of time, transition metal-mediated radiofluorination reactions have changed the PET radiochemistry landscape. These reactions have enabled the radiofluorination of a wide range of substrates, facilitating access to radiopharmaceuticals that were challenging to synthesize using traditional fluorine-18 radiochemistry. However, the process of adapting these new reactions for automated radiopharmaceutical production has revealed limitations in fitting them into the confines of traditional radiochemistry systems. In particular, the presence of bases (e.g. K 2CO 3) and/or phase transfer catalysts (PTC) (e.g. kryptofix 2.2.2) associated with fluorine-18 preparation has been found to be detrimental to reaction yields. We hypothesizedmore » that these limitations could be addressed through the development of alternate techniques for preparing [18F]fluoride. This approach also opens the possibility that an eluent can be individually tailored to meet the specific needs of a metal-catalyzed reaction of interest. In this communication, we demonstrate that various solutions of copper salts, bases, and ancillary ligands can be utilized to elute [ 18F]fluoride from ion exchange cartridges. The new procedures we present here are effective for fluorine-18 radiochemistry and, as proof of concept, have been used to optimize an otherwise base-sensitive copper-mediated radiofluorination reaction.« less

Development of Customized [18F]Fluoride Elution Techniques for the Enhancement of Copper-Mediated Late-Stage Radiofluorination

DOE PAGES

Mossine, Andrew V.; Brooks, Allen F.; Ichiishi, Naoko; ...

2017-03-22

In a relatively short period of time, transition metal-mediated radiofluorination reactions have changed the PET radiochemistry landscape. These reactions have enabled the radiofluorination of a wide range of substrates, facilitating access to radiopharmaceuticals that were challenging to synthesize using traditional fluorine-18 radiochemistry. However, the process of adapting these new reactions for automated radiopharmaceutical production has revealed limitations in fitting them into the confines of traditional radiochemistry systems. In particular, the presence of bases (e.g. K 2CO 3) and/or phase transfer catalysts (PTC) (e.g. kryptofix 2.2.2) associated with fluorine-18 preparation has been found to be detrimental to reaction yields. We hypothesizedmore » that these limitations could be addressed through the development of alternate techniques for preparing [18F]fluoride. This approach also opens the possibility that an eluent can be individually tailored to meet the specific needs of a metal-catalyzed reaction of interest. In this communication, we demonstrate that various solutions of copper salts, bases, and ancillary ligands can be utilized to elute [ 18F]fluoride from ion exchange cartridges. The new procedures we present here are effective for fluorine-18 radiochemistry and, as proof of concept, have been used to optimize an otherwise base-sensitive copper-mediated radiofluorination reaction.« less

No evidence of reaction time slowing in autism spectrum disorder.

PubMed

Ferraro, F Richard

2016-01-01

A total of 32 studies comprising 238 simple reaction time and choice reaction time conditions were examined in individuals with autism spectrum disorder (n = 964) and controls (n = 1032). A Brinley plot/multiple regression analysis was performed on mean reaction times, regressing autism spectrum disorder performance onto the control performance as a way to examine any generalized simple reaction time/choice reaction time slowing exhibited by the autism spectrum disorder group. The resulting regression equation was Y (autism spectrum disorder) = 0.99 × (control) + 87.93, which accounted for 92.3% of the variance. These results suggest that there are little if any simple reaction time/choice reaction time slowing in this sample of individual with autism spectrum disorder, in comparison with controls. While many cognitive and information processing domains are compromised in autism spectrum disorder, it appears that simple reaction time/choice reaction time remain relatively unaffected in autism spectrum disorder. © The Author(s) 2014.

Solving of the coefficient inverse problems for a nonlinear singularly perturbed reaction-diffusion-advection equation with the final time data

NASA Astrophysics Data System (ADS)

Lukyanenko, D. V.; Shishlenin, M. A.; Volkov, V. T.

2018-01-01

We propose the numerical method for solving coefficient inverse problem for a nonlinear singularly perturbed reaction-diffusion-advection equation with the final time observation data based on the asymptotic analysis and the gradient method. Asymptotic analysis allows us to extract a priory information about interior layer (moving front), which appears in the direct problem, and boundary layers, which appear in the conjugate problem. We describe and implement the method of constructing a dynamically adapted mesh based on this a priory information. The dynamically adapted mesh significantly reduces the complexity of the numerical calculations and improve the numerical stability in comparison with the usual approaches. Numerical example shows the effectiveness of the proposed method.

Paper-Plastic Hybrid Microfluidic Device for Smartphone-Based Colorimetric Analysis of Urine.

PubMed

Jalal, Uddin M; Jin, Gyeong Jun; Shim, Joon S

2017-12-19

In this work, a disposable paper-plastic hybrid microfluidic lab-on-a-chip (LOC) has been developed and successfully applied for the colorimetric measurement of urine by the smartphone-based optical platform using a "UrineAnalysis" Android app. The developed device was cost-effectively implemented as a stand-alone hybrid LOC by incorporating the paper-based conventional reagent test strip inside the plastic-based LOC microchannel. The LOC device quantitatively investigated the small volume (40 μL) of urine analytes for the colorimetric reaction of glucose, protein, pH, and red blood cell (RBC) in integration with the finger-actuating micropump. On the basis of our experiments, the conventional urine strip showed large deviation as the reaction time goes by, because dipping the strip sensor in a bottle of urine could not control the reaction volume. By integrating the strip sensor in the LOC device for urine analysis, our device significantly improves the time-dependent inconstancy of the conventional dipstick-based urine strip, and the smartphone app used for image analysis enhances the visual assessment of the test strip, which is a major user concern for the colorimetric analysis in point-of-care (POC) applications. As a result, the user-friendly LOC, which is successfully implemented in a disposable format with the smartphone-based optical platform, may be applicable as an effective tool for rapid and qualitative POC urinalysis.

A new use of hydroxyapatite-based consolidant: cleaning and consolidation of stones in one step by reaction with gypsum crust

NASA Astrophysics Data System (ADS)

Molina Piernas, Eduardo; Rueda Quero, Lucia; Cultrone, Giuseppe; Ruiz Agudo, Encarnación

2015-04-01

The reaction between diammonium hydrogen phosphate (DAP) and calcite in the stone to form hydroxyapatite (HAP) had provided a new product to consolidate limestone or Ca-rich stones, for example sandstones with carbonatic cement. However, what does it happen with the stones without Ca-bearing compounds? Obviously, HAP cannot form. In the other hand, recent research about consolidation with DAP show a good interaction between carbonatic stones and HAP, improving their mechanical properties. For these reasons, we propose a new method for the consolidation of building stone capable of cleaning the gypsum crust and consolidating stones at the same time, based in the Ferroni-Dini method [1] and using DAP. Based on this method, we aim at obtaining a consolidating component reacting DAP (instead of ammonium carbonate) and the gypsum contained in the crust of weathered stones in polluted environments. As an advantage, we do not need to use barium hydroxide (the second step required in the Ferroni-Dini method), thereby reducing the time necessary to carry out the consolidation. Here, we report different tests to evaluate this new procedure. In a first set of experiments, a DAP solution was poured on a gypsum (dihydrate calcium sulphate) saturated solution and by monitoring the free calcium content of the solution using an ion-selective electrode we have evaluated the fluctuations in the content in calcium of the solution and the speed of the reaction. Once the reaction finished, we analyzed the solids formed to verify the formation of hydroxyapatite by FTIR and microRAMAN. The second test consisted in the alteration of limestone blocks with sulfuric acid to obtain a crust of gypsum and, after that, the samples were consolidated by means of cellulose compress soaked in DAP 3M during different reaction times (30 minutes, 1 hour and 4 hours, at controlled temperature -20 °C- and relative humidity -40% HR-). The samples were then analyzed by XRD, FTIR, microRAMAN and SEM-EDX to verify the formation of hydroxyapatite and the elimination of gypsum by transformation into ammonium sulphate (highly soluble). Our preliminary results show that the reaction occurs at room temperature in a short period of time. The amount of gypsum decreases with reaction time, while the amount of HAP significantly increases, with the gypsum being almost completely removed after 4 hours of reaction. We can conclude that this procedure is an optimal solution to remove the gypsum contained in the crust of the weathered stones and to consolidate them, independently of the mineralogical composition of the stone. Acknowledgements: This study was financially supported by Research Group RNM179 of the Junta de Andalucía and by the Research Project MAT2012-34473. [1] M. Matteini, "In review: An assessment of Florentine Methods of Wall Painting Conservation Based on the Use of Mineral Treatments", in "The Conservation of Wall Paintings: Proceedings of a Symposium organized by the Courtauld Institute of Art and the Getty Conservation Institute", London, 1987, pp. 137-146.

A fluorescence high throughput screening method for the detection of reactive electrophiles as potential skin sensitizers

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

Avonto, Cristina; Chittiboyina, Amar G.; Rua, Diego

2015-12-01

Skin sensitization is an important toxicological end-point in the risk assessment of chemical allergens. Because of the complexity of the biological mechanisms associated with skin sensitization, integrated approaches combining different chemical, biological and in silico methods are recommended to replace conventional animal tests. Chemical methods are intended to characterize the potential of a sensitizer to induce earlier molecular initiating events. The presence of an electrophilic mechanistic domain is considered one of the essential chemical features to covalently bind to the biological target and induce further haptenation processes. Current in chemico assays rely on the quantification of unreacted model nucleophiles aftermore » incubation with the candidate sensitizer. In the current study, a new fluorescence-based method, ‘HTS-DCYA assay’, is proposed. The assay aims at the identification of reactive electrophiles based on their chemical reactivity toward a model fluorescent thiol. The reaction workflow enabled the development of a High Throughput Screening (HTS) method to directly quantify the reaction adducts. The reaction conditions have been optimized to minimize solubility issues, oxidative side reactions and increase the throughput of the assay while minimizing the reaction time, which are common issues with existing methods. Thirty-six chemicals previously classified with LLNA, DPRA or KeratinoSens™ were tested as a proof of concept. Preliminary results gave an estimated 82% accuracy, 78% sensitivity, 90% specificity, comparable to other in chemico methods such as Cys-DPRA. In addition to validated chemicals, six natural products were analyzed and a prediction of their sensitization potential is presented for the first time. - Highlights: • A novel fluorescence-based method to detect electrophilic sensitizers is proposed. • A model fluorescent thiol was used to directly quantify the reaction products. • A discussion of the reaction workflow and critical parameters is presented. • The method could provide a useful tool to complement existing chemical assays.« less

Lack of correlation between reaction speed and analytical sensitivity in isothermal amplification reveals the value of digital methods for optimization: validation using digital real-time RT-LAMP.

PubMed

Khorosheva, Eugenia M; Karymov, Mikhail A; Selck, David A; Ismagilov, Rustem F

2016-01-29

In this paper, we asked if it is possible to identify the best primers and reaction conditions based on improvements in reaction speed when optimizing isothermal reactions. We used digital single-molecule, real-time analyses of both speed and efficiency of isothermal amplification reactions, which revealed that improvements in the speed of isothermal amplification reactions did not always correlate with improvements in digital efficiency (the fraction of molecules that amplify) or with analytical sensitivity. However, we observed that the speeds of amplification for single-molecule (in a digital device) and multi-molecule (e.g. in a PCR well plate) formats always correlated for the same conditions. Also, digital efficiency correlated with the analytical sensitivity of the same reaction performed in a multi-molecule format. Our finding was supported experimentally with examples of primer design, the use or exclusion of loop primers in different combinations, and the use of different enzyme mixtures in one-step reverse-transcription loop-mediated amplification (RT-LAMP). Our results show that measuring the digital efficiency of amplification of single-template molecules allows quick, reliable comparisons of the analytical sensitivity of reactions under any two tested conditions, independent of the speeds of the isothermal amplification reactions. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

Force modeling for incisions into various tissues with MRF haptic master

NASA Astrophysics Data System (ADS)

Kim, Pyunghwa; Kim, Soomin; Park, Young-Dai; Choi, Seung-Bok

2016-03-01

This study proposes a new model to predict the reaction force that occurs in incisions during robot-assisted minimally invasive surgery. The reaction force is fed back to the manipulator by a magneto-rheological fluid (MRF) haptic master, which is featured by a bi-directional clutch actuator. The reaction force feedback provides similar sensations to laparotomy that cannot be provided by a conventional master for surgery. This advantage shortens the training period for robot-assisted minimally invasive surgery and can improve the accuracy of operations. The reaction force modeling of incisions can be utilized in a surgical simulator that provides a virtual reaction force. In this work, in order to model the reaction force during incisions, the energy aspect of the incision process is adopted and analyzed. Each mode of the incision process is classified by the tendency of the energy change, and modeled for realistic real-time application. The reaction force model uses actual reaction force information with three types of actual tissues: hard tissue, medium tissue, and soft tissue. This modeled force is realized by the MRF haptic master through an algorithm based on the position and velocity of a scalpel using two different control methods: an open-loop algorithm and a closed-loop algorithm. The reaction forces obtained from the proposed model are compared with a desired force in time domain.

Effect of reaction time and polyethylene glycol monooleate-isocyanate composition on the properties of polyurethane-polysiloxane modified epoxy

NASA Astrophysics Data System (ADS)

Triwulandari, Evi; Ramadhan, Mohammad Kemilau; Ghozali, Muhammad

2017-11-01

Polyurethane-polysiloxane modified epoxy based on polyethylene glycol monooleate (PSME-PEGMO) was synthesized. Polyethylene glycol monooleate (PEGMO) for the synthesis of PSME-GMO was synthesized via esterification between oleic acid and polyethylene glycol by using sodium hydroxide as catalyst. Synthesis of PSME-PEGMO was conducted by reacting epoxy, isocyanate, PEGMO, and polysiloxane (hydrolyzed and condensable 3-glycidyloxypropyltrimethoxysilane) simultaneously in one step. This synthesis was carried out by varied the reaction time (1, 2, 3 hours), PEGMO-isocyanate composition (PI composition: 10 and 20 % toward epoxy), and isocyanate/PEGMO ratio (NCO/OH ratio: 1.5 and 2.5). Characterization of PSME-PEGMO was conducted by determining the isocyanate conversion, viscosity analysis, mechanical properties (tensile strength and elongation at break) and thermal analysis using thermogravimetric analysis (TGA). The data show that the PI composition and NCO/OH ratio does not affect the isocyanate conversion linearly. The viscosity of PSME-PEGMO product at ratio and composition variation show has tended to increase with increasing of reaction time. The highest tensile strength and elongation at break PSME-PEGMO was shown by PI composition 20%, NCO/OH ratio 2.5 and reaction time 3 hours.

Modelling Chemical Reasoning to Predict and Invent Reactions.

PubMed

Segler, Marwin H S; Waller, Mark P

2017-05-02

The ability to reason beyond established knowledge allows organic chemists to solve synthetic problems and invent novel transformations. Herein, we propose a model that mimics chemical reasoning, and formalises reaction prediction as finding missing links in a knowledge graph. We have constructed a knowledge graph containing 14.4 million molecules and 8.2 million binary reactions, which represents the bulk of all chemical reactions ever published in the scientific literature. Our model outperforms a rule-based expert system in the reaction prediction task for 180 000 randomly selected binary reactions. The data-driven model generalises even beyond known reaction types, and is thus capable of effectively (re-)discovering novel transformations (even including transition metal-catalysed reactions). Our model enables computers to infer hypotheses about reactivity and reactions by only considering the intrinsic local structure of the graph and because each single reaction prediction is typically achieved in a sub-second time frame, the model can be used as a high-throughput generator of reaction hypotheses for reaction discovery. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Acid–base catalysis over perovskites: a review

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

Polo-Garzon, Felipe; Wu, Zili

We present that perovskite catalysts have been extensively studied for reduction–oxidation (redox) reactions; however, their acid–base catalytic properties are still under-explored. This review collects work aiming to study the acid–base catalytic properties of perovskites. Reports regarding combined acid–base/redox catalysis over perovskites lie beyond the scope of the present review. For the characterization of acid–base properties, researchers have studied the interaction of probe molecules with perovskite surfaces by means of multiple techniques that provide information about the density, strength and type of adsorption sites. The top-surface composition of perovskites, which relates to the abundance of the acid–base sites, has been studiedmore » by means of low energy ion scattering (LEIS), and, the less surface sensitive, conventional X-ray photoelectron spectroscopy (XPS). Probe reactions, with the conversion of 2-propanol as the common choice, have also been employed for characterizing the acid–base catalytic properties of perovskites. The complex nature of perovskite surfaces, which explains the still absent fundamental relations between the structure of the catalyst and reaction rates/selectivity, encounters a great challenge due to the surface reconstruction of these materials. In this review, we devote a special section to highlight recent publications that report the impact of surface reconstruction and particle shape on acid–base catalysis over perovskites. In addition, we review promising catalytic performances of perovskite catalysts for other reactions of interest. Challenges in acid–base catalysis over perovskites focus on the development of time-resolved monolayer-sensitive characterization of surfaces under operando conditions and the discernment of combined acid–base/redox reaction mechanisms. Finally, opportunities lay on tuning the acid–base characteristics of perovskites with computation-based catalytic descriptors to achieve desired selectivities and enhanced rates.« less

Acid–base catalysis over perovskites: a review

DOE PAGES

Polo-Garzon, Felipe; Wu, Zili

2018-01-15

We present that perovskite catalysts have been extensively studied for reduction–oxidation (redox) reactions; however, their acid–base catalytic properties are still under-explored. This review collects work aiming to study the acid–base catalytic properties of perovskites. Reports regarding combined acid–base/redox catalysis over perovskites lie beyond the scope of the present review. For the characterization of acid–base properties, researchers have studied the interaction of probe molecules with perovskite surfaces by means of multiple techniques that provide information about the density, strength and type of adsorption sites. The top-surface composition of perovskites, which relates to the abundance of the acid–base sites, has been studiedmore » by means of low energy ion scattering (LEIS), and, the less surface sensitive, conventional X-ray photoelectron spectroscopy (XPS). Probe reactions, with the conversion of 2-propanol as the common choice, have also been employed for characterizing the acid–base catalytic properties of perovskites. The complex nature of perovskite surfaces, which explains the still absent fundamental relations between the structure of the catalyst and reaction rates/selectivity, encounters a great challenge due to the surface reconstruction of these materials. In this review, we devote a special section to highlight recent publications that report the impact of surface reconstruction and particle shape on acid–base catalysis over perovskites. In addition, we review promising catalytic performances of perovskite catalysts for other reactions of interest. Challenges in acid–base catalysis over perovskites focus on the development of time-resolved monolayer-sensitive characterization of surfaces under operando conditions and the discernment of combined acid–base/redox reaction mechanisms. Finally, opportunities lay on tuning the acid–base characteristics of perovskites with computation-based catalytic descriptors to achieve desired selectivities and enhanced rates.« less

HRSSA – Efficient hybrid stochastic simulation for spatially homogeneous biochemical reaction networks

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

Marchetti, Luca, E-mail: marchetti@cosbi.eu; Priami, Corrado, E-mail: priami@cosbi.eu; University of Trento, Department of Mathematics

This paper introduces HRSSA (Hybrid Rejection-based Stochastic Simulation Algorithm), a new efficient hybrid stochastic simulation algorithm for spatially homogeneous biochemical reaction networks. HRSSA is built on top of RSSA, an exact stochastic simulation algorithm which relies on propensity bounds to select next reaction firings and to reduce the average number of reaction propensity updates needed during the simulation. HRSSA exploits the computational advantage of propensity bounds to manage time-varying transition propensities and to apply dynamic partitioning of reactions, which constitute the two most significant bottlenecks of hybrid simulation. A comprehensive set of simulation benchmarks is provided for evaluating performance andmore » accuracy of HRSSA against other state of the art algorithms.« less

Synthesis of Transesterified Palm Olein-Based Polyol and Rigid Polyurethanes from this Polyol.

PubMed

Arniza, Mohd Zan; Hoong, Seng Soi; Idris, Zainab; Yeong, Shoot Kian; Hassan, Hazimah Abu; Din, Ahmad Kushairi; Choo, Yuen May

Transesterification of palm olein with glycerol can increase the functionality by introducing additional hydroxyl groups to the triglyceride structure, an advantage compared to using palm olein directly as feedstock for producing palm-based polyol. The objective of this study was to synthesize transesterified palm olein-based polyol via a three-step reaction: (1) transesterification of palm olein, (2) epoxidation and (3) epoxide ring opening. Transesterification of palm olein yielded approximately 78 % monoglyceride and has an hydroxyl value of approximately 164 mg KOH g -1 . The effect of formic acid and hydrogen peroxide concentrations on the epoxidation reaction was studied. The relationships between epoxide ring-opening reaction time and residual oxirane oxygen content and hydroxyl value were monitored. The synthesized transesterified palm olein-based polyol has hydroxyl value between 300 and 330 mg KOH g -1 and average molecular weight between 1,000 and 1,100 Da. On the basis of the hydroxyl value and average molecular weight of the polyol, the transesterified palm olein-based polyol is suitable for producing rigid polyurethane foam, which can be designed to exhibit desirable properties. Rigid polyurethane foams were synthesized by substituting a portion of petroleum-based polyol with the transesterified palm olein-based polyol. It was observed that by increasing the amount of transesterified palm olein-based polyol, the core density and compressive strength were reduced but at the same time the insulation properties of the rigid polyurethane foam were improved.

Rayleigh surface acoustic wave as an efficient heating system for biological reactions: investigation of microdroplet temperature uniformity.

PubMed

Roux-Marchand, Thibaut; Beyssen, Denis; Sarry, Frederic; Elmazria, Omar

2015-04-01

When a microdroplet is put on the Rayleigh surface acoustic wave path, longitudinal waves are radiated into the liquid and induce several phenomena such as the wellknown surface acoustic wave streaming. At the same time, the temperature of the microdroplet increases as it has been shown. In this paper, we study the temperature uniformity of a microdroplet heated by Rayleigh surface acoustic wave for discrete microfluidic applications such as biological reactions. To precisely ascertain the temperature uniformity and not interfere with the biological reaction, we used an infrared camera. We then tested the temperature uniformity as a function of three parameters: the microdroplet volume, the Rayleigh surface acoustic wave frequency, and the continuous applied radio frequency power. Based on these results, we propose a new device structure to develop a future lab on a chip based on reaction temperatures.

Adverse events related to blood transfusion

PubMed Central

Sahu, Sandeep; Hemlata; Verma, Anupam

2014-01-01

The acute blood transfusion reactions are responsible for causing most serious adverse events. Awareness about various clinical features of acute and delayed transfusion reactions with an ability to assess the serious reactions on time can lead to a better prognosis. Evidence-based medicine has changed today's scenario of clinical practice to decrease adverse transfusion reactions. New evidence-based algorithms of transfusion and improved haemovigilance lead to avoidance of unnecessary transfusions perioperatively. The recognition of adverse events under anaesthesia is always challenging. The unnecessary blood transfusions can be avoided with better blood conservation techniques during surgery and with anaesthesia techniques that reduce blood loss. Better and newer blood screening methods have decreased the infectious complications to almost negligible levels. With universal leukoreduction of red blood cells (RBCs), selection of potential donors such as use of male donors only plasma and restriction of RBC storage, most of the non-infectious complications can be avoided. PMID:25535415

Using Multiorder Time-Correlation Functions (TCFs) To Elucidate Biomolecular Reaction Pathways from Microsecond Single-Molecule Fluorescence Experiments.

PubMed

Phelps, Carey; Israels, Brett; Marsh, Morgan C; von Hippel, Peter H; Marcus, Andrew H

2016-12-29

Recent advances in single-molecule fluorescence imaging have made it possible to perform measurements on microsecond time scales. Such experiments have the potential to reveal detailed information about the conformational changes in biological macromolecules, including the reaction pathways and dynamics of the rearrangements involved in processes, such as sequence-specific DNA "breathing" and the assembly of protein-nucleic acid complexes. Because microsecond-resolved single-molecule trajectories often involve "sparse" data, that is, they contain relatively few data points per unit time, they cannot be easily analyzed using the standard protocols that were developed for single-molecule experiments carried out with tens-of-millisecond time resolution and high "data density." Here, we describe a generalized approach, based on time-correlation functions, to obtain kinetic information from microsecond-resolved single-molecule fluorescence measurements. This approach can be used to identify short-lived intermediates that lie on reaction pathways connecting relatively long-lived reactant and product states. As a concrete illustration of the potential of this methodology for analyzing specific macromolecular systems, we accompany the theoretical presentation with the description of a specific biologically relevant example drawn from studies of reaction mechanisms of the assembly of the single-stranded DNA binding protein of the T4 bacteriophage replication complex onto a model DNA replication fork.

Enhanced reaction kinetics and reactive mixing scale dynamics in mixing fronts under shear flow for arbitrary Damköhler numbers

NASA Astrophysics Data System (ADS)

Bandopadhyay, Aditya; Le Borgne, Tanguy; Méheust, Yves; Dentz, Marco

2017-02-01

Mixing fronts, where fluids of different chemical compositions mix with each other, are known to represent hotspots of chemical reaction in hydrological systems. These fronts are typically subjected to velocity gradients, ranging from the pore scale due to no slip boundary conditions at fluid solid interfaces, to the catchment scale due to permeability variations and complex geometry of the Darcy velocity streamlines. A common trait of these processes is that the mixing interface is strained by shear. Depending on the Péclet number Pe , which represents the ratio of the characteristic diffusion time to the characteristic shear time, and the Damköhler number Da , which represents the ratio of the characteristic diffusion time to the characteristic reaction time, the local reaction rates can be strongly impacted by the dynamics of the mixing interface. So far, this impact has been characterized mostly either in kinetics-limited or in mixing-limited conditions, that is, for either low or high Da. Here the coupling of shear flow and chemical reactivity is investigated for arbitrary Damköhler numbers, for a bimolecular reaction and an initial interface with separated reactants. Approximate analytical expressions for the global production rate and reactive mixing scale are derived based on a reactive lamella approach that allows for a general coupling between stretching enhanced mixing and chemical reactions. While for Pe < Da , reaction kinetics and stretching effects are decoupled, a scenario which we name "weak stretching", for Pe > Da , we uncover a "strong stretching" scenario where new scaling laws emerge from the interplay between reaction kinetics, diffusion, and stretching. The analytical results are validated against numerical simulations. These findings shed light on the effect of flow heterogeneity on the enhancement of chemical reaction and the creation of spatially localized hotspots of reactivity for a broad range of systems ranging from kinetic limited to mixing limited situations.

Reaction time, impulsivity, and attention in hyperactive children and controls: a video game technique.

PubMed

Mitchell, W G; Chavez, J M; Baker, S A; Guzman, B L; Azen, S P

1990-07-01

Maturation of sustained attention was studied in a group of 52 hyperactive elementary school children and 152 controls using a microcomputer-based test formatted to resemble a video game. In nonhyperactive children, both simple and complex reaction time decreased with age, as did variability of response time. Omission errors were extremely infrequent on simple reaction time and decreased with age on the more complex tasks. Commission errors had an inconsistent relationship with age. Hyperactive children were slower, more variable, and made more errors on all segments of the game than did controls. Both motor speed and calculated mental speed were slower in hyperactive children, with greater discrepancy for responses directed to the nondominant hand, suggesting that a selective right hemisphere deficit may be present in hyperactives. A summary score (number of individual game scores above the 95th percentile) of 4 or more detected 60% of hyperactive subjects with a false positive rate of 5%. Agreement with the Matching Familiar Figures Test was 75% in the hyperactive group.

Improvements in Concentration, Working Memory, and Sustained Attention Following Consumption of a Natural Citicoline-Caffeine Beverage

PubMed Central

Bruce, Steven E.; Werner, Kimberly B.; Preston, Brittany F.; Baker, Laurie M.

2015-01-01

The present study examined the neurocognitive and electrophysiological effects of a citicoline-caffeine-based beverage in 60 healthy adult participants enrolled in a randomized, double-blind, placebo-controlled trial. Measures of electrical brain activity using electroencephalogram (EEG) and neuropsychological measures examining attention, concentration, and reaction time were administered. Compared to placebo, participants receiving the citicoline-caffeine beverage exhibited significantly faster maze learning times and reaction times on a continuous performance test, fewer errors in a Go No-Go task, and better accuracy on a measure of information processing speed. EEG results examining P450 event related potentials (ERP) revealed that participants receiving the citicoline-caffeine beverage exhibited higher P450 amplitudes than controls, suggesting an increase in sustained attention. Overall, these findings suggest that the beverage significantly improved sustained attention, cognitive effort, and reaction times in healthy adults. Evidence of improved P450 amplitude indicates a general improvement in the ability to accommodate new and relevant information within working memory and overall enhanced brain activation. PMID:25046515

Unsupervised spatiotemporal analysis of fMRI data using graph-based visualizations of self-organizing maps.

PubMed

Katwal, Santosh B; Gore, John C; Marois, Rene; Rogers, Baxter P

2013-09-01

We present novel graph-based visualizations of self-organizing maps for unsupervised functional magnetic resonance imaging (fMRI) analysis. A self-organizing map is an artificial neural network model that transforms high-dimensional data into a low-dimensional (often a 2-D) map using unsupervised learning. However, a postprocessing scheme is necessary to correctly interpret similarity between neighboring node prototypes (feature vectors) on the output map and delineate clusters and features of interest in the data. In this paper, we used graph-based visualizations to capture fMRI data features based upon 1) the distribution of data across the receptive fields of the prototypes (density-based connectivity); and 2) temporal similarities (correlations) between the prototypes (correlation-based connectivity). We applied this approach to identify task-related brain areas in an fMRI reaction time experiment involving a visuo-manual response task, and we correlated the time-to-peak of the fMRI responses in these areas with reaction time. Visualization of self-organizing maps outperformed independent component analysis and voxelwise univariate linear regression analysis in identifying and classifying relevant brain regions. We conclude that the graph-based visualizations of self-organizing maps help in advanced visualization of cluster boundaries in fMRI data enabling the separation of regions with small differences in the timings of their brain responses.

Improved synthesis of phosphatidylserine using bio-based solvents, limonene and p-cymene.

PubMed

Bi, Yan-Hong; Duan, Zhang-Qun; Du, Wen-Ying; Wang, Zhao-Yu

2015-01-01

The bio-based solvents limonene and p-cymene obtained from citrus waste were innovatively employed as the reaction media for enzymatic synthesis of phosphatidylserine. (R)-(+)-Limonene, which is available in large quantities from citrus waste, and its close derivative p-cymene, are promising green solvents. Herein, they were successfully employed as reaction media for enzyme-mediated transphosphatidylation of phosphatidylcholine with L-serine for phosphatidylserine synthesis for the first time. A 95 % yield of phosphatidylserine was achieved after 12 h and the side-reactions (which are the undesirable hydrolysis of phosphatidylcholine and phosphatidylserine) did not happen. This work presents an alternative strategy for preparing phosphatidylserine that possesses obvious advantages over the traditional processes in terms of high efficiency combined with environmental friendliness.

Analysis of parameter and interaction between parameter of the microwave assisted transesterification process of coconut oil using response surface methodology

NASA Astrophysics Data System (ADS)

Hidayanti, Nur; Suryanto, A.; Qadariyah, L.; Prihatini, P.; Mahfud, Mahfud

2015-12-01

A simple batch process was designed for the transesterification of coconut oil to alkyl esters using microwave assisted method. The product with yield above 93.225% of alkyl ester is called the biodiesel fuel. Response surface methodology was used to design the experiment and obtain the maximum possible yield of biodiesel in the microwave-assisted reaction from coconut oil with KOH as the catalyst. The results showed that the time reaction and concentration of KOH catalyst have significant effects on yield of alkyl ester. Based on the response surface methodology using the selected operating conditions, the time of reaction and concentration of KOH catalyst in transesterification process were 150 second and 0.25%w/w, respectively. The largest predicted and experimental yield of alkyl esters (biodiesel) under the optimal conditions are 101.385% and 93.225%, respectively. Our findings confirmed the successful development of process for the transesterification reaction of coconut oil by microwave-assisted heating, which is effective and time-saving for alkyl ester production.

Soft tissue deformation modelling through neural dynamics-based reaction-diffusion mechanics.

PubMed

Zhang, Jinao; Zhong, Yongmin; Gu, Chengfan

2018-05-30

Soft tissue deformation modelling forms the basis of development of surgical simulation, surgical planning and robotic-assisted minimally invasive surgery. This paper presents a new methodology for modelling of soft tissue deformation based on reaction-diffusion mechanics via neural dynamics. The potential energy stored in soft tissues due to a mechanical load to deform tissues away from their rest state is treated as the equivalent transmembrane potential energy, and it is distributed in the tissue masses in the manner of reaction-diffusion propagation of nonlinear electrical waves. The reaction-diffusion propagation of mechanical potential energy and nonrigid mechanics of motion are combined to model soft tissue deformation and its dynamics, both of which are further formulated as the dynamics of cellular neural networks to achieve real-time computational performance. The proposed methodology is implemented with a haptic device for interactive soft tissue deformation with force feedback. Experimental results demonstrate that the proposed methodology exhibits nonlinear force-displacement relationship for nonlinear soft tissue deformation. Homogeneous, anisotropic and heterogeneous soft tissue material properties can be modelled through the inherent physical properties of mass points. Graphical abstract Soft tissue deformation modelling with haptic feedback via neural dynamics-based reaction-diffusion mechanics.

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

Sun, Junming; Baylon, Rebecca A.; Liu, Changjun

The effects of surface acidity on the cascade ethanol-to-isobutene conversion were studied using ZnxZryOz catalysts. The ethanol-to-isobutene reaction was found to be limited by the secondary reaction of the key intermediate, acetone, namely the acetone-to-isobutene reaction. Although the catalysts with coexisting Brønsted acidity could catalyze the rate-limiting acetone-to-isobutene reaction, the presence of Brønsted acidity is also detrimental. First, secondary isobutene isomerization is favored, producing a mixture of butene isomers. Second, undesired polymerization and coke formation prevail, leading to rapid catalyst deactivation. Most importantly, both steady-state and kinetic reaction studies as well as FTIR analysis of adsorbed acetone-d6 and D2O unambiguouslymore » showed that a highly active and selective nature of balanced Lewis acid-base pairs was masked by the coexisting Brønsted acidity in the aldolization and self-deoxygenation of acetone to isobutene. As a result, ZnxZryOz catalysts with only Lewis acid-base pairs were discovered, on which nearly a theoretical selectivity to isobutene (~88.9%) was successfully achieved, which has never been reported before. Moreover, the absence of Brønsted acidity in such ZnxZryOz catalysts also eliminates the side isobutene isomerization and undesired polymerization/coke reactions, resulting in the production of high purity isobutene with significantly improved catalyst stability (< 2% activity loss after 200 h time-on-stream). This work not only demonstrates a balanced Lewis acid-base pair for the highly active and selective cascade ethanol-to-isobutene reaction, but also sheds light on the rational design of selective and robust acid-base catalyst for C-C coupling via aldolization reaction.« less

One-step simultaneous differential scanning calorimetry-FTIR microspectroscopy to quickly detect continuous pathways in the solid-state glucose/asparagine Maillard reaction.

PubMed

Hwang, Deng-Fwu; Hsieh, Tzu-Feng; Lin, Shan-Yang

2013-01-01

The stepwise reaction pathway of the solid-state Maillard reaction between glucose (Glc) and asparagine (Asn) was investigated using simultaneous differential scanning calorimetry (DSC)-FTIR microspectroscopy. The color change and FTIR spectra of Glc-Asn physical mixtures (molar ratio = 1:1) preheated to different temperatures followed by cooling were also examined. The successive reaction products such as Schiff base intermediate, Amadori product, and decarboxylated Amadori product in the solid-state Glc-Asn Maillard reaction were first simultaneously evidenced by this unique DSC-FTIR microspectroscopy. The color changed from white to yellow-brown to dark brown, and appearance of new IR peaks confirmed the formation of Maillard reaction products. The present study clearly indicates that this unique DSC-FTIR technique not only accelerates but also detects precursors and products of the Maillard reaction in real time.

Genotype identification of Math1/LacZ knockout mice based on real-time PCR with SYBR Green I dye.

PubMed

Krizhanovsky, Valery; Golenser, Esther; Ben-Arie, Nissim

2004-07-30

Knockout mice are widely used in all fields of biomedical research. Determining the genotype of every newborn mouse is a tedious task, usually performed by Southern blot hybridization or Polymerase Chain Reaction (PCR). We describe here a quick and simple genotype identification assay based on real-time PCR and SYBR Green I dye, without using fluorescent primers. The discrimination between the wild type and targeted alleles is based on a PCR design that leads to a different melting temperature for each product. The identification of the genotype is obvious immediately after amplification, and no post-PCR manipulations are needed, reducing cost and time. Therefore, while the real-time PCR amplification increases the sensitivity, the fact that the reactions tubes are never opened after amplification, reduces the risk of contamination and eliminates errors, which are common during the repeated handling of dozens of samples from the same mouse line. The protocol we provide was tested on Math1 knockout mice, but is general, and may be utilized for any knockout line and real-time thermocycler, without any further modification, accessories or special reagents. Copyright 2004 Elsevier B.V.

Synthesis of a new class of Betti bases by the Mannich-type reaction: efficient, facile, solvent-free and one-pot protocol.

PubMed

Shahrisa, Aziz; Teimuri-Mofrad, Reza; Gholamhosseini-Nazari, Mahdi

2015-02-01

A variety of organocatalysts has been screened for the synthesis of arylaminonaphthols. It has been shown that (N,N-dimethylethanolamine) is a highly efficient organocatalyst for the direct synthesis of a novel class of arylaminonaphthols via three-component condensation of 2-naphthol, aldehydes, and arylamines under solvent-free conditions. Mild, one-pot, and green reaction conditions, relatively short reaction times and good yields make this protocol highly significant. 25 new compounds have been synthesized by this method.

Simulation of reaction diffusion processes over biologically relevant size and time scales using multi-GPU workstations

PubMed Central

Hallock, Michael J.; Stone, John E.; Roberts, Elijah; Fry, Corey; Luthey-Schulten, Zaida

2014-01-01

Simulation of in vivo cellular processes with the reaction-diffusion master equation (RDME) is a computationally expensive task. Our previous software enabled simulation of inhomogeneous biochemical systems for small bacteria over long time scales using the MPD-RDME method on a single GPU. Simulations of larger eukaryotic systems exceed the on-board memory capacity of individual GPUs, and long time simulations of modest-sized cells such as yeast are impractical on a single GPU. We present a new multi-GPU parallel implementation of the MPD-RDME method based on a spatial decomposition approach that supports dynamic load balancing for workstations containing GPUs of varying performance and memory capacity. We take advantage of high-performance features of CUDA for peer-to-peer GPU memory transfers and evaluate the performance of our algorithms on state-of-the-art GPU devices. We present parallel e ciency and performance results for simulations using multiple GPUs as system size, particle counts, and number of reactions grow. We also demonstrate multi-GPU performance in simulations of the Min protein system in E. coli. Moreover, our multi-GPU decomposition and load balancing approach can be generalized to other lattice-based problems. PMID:24882911

Simulation of reaction diffusion processes over biologically relevant size and time scales using multi-GPU workstations.

PubMed

Hallock, Michael J; Stone, John E; Roberts, Elijah; Fry, Corey; Luthey-Schulten, Zaida

2014-05-01

Simulation of in vivo cellular processes with the reaction-diffusion master equation (RDME) is a computationally expensive task. Our previous software enabled simulation of inhomogeneous biochemical systems for small bacteria over long time scales using the MPD-RDME method on a single GPU. Simulations of larger eukaryotic systems exceed the on-board memory capacity of individual GPUs, and long time simulations of modest-sized cells such as yeast are impractical on a single GPU. We present a new multi-GPU parallel implementation of the MPD-RDME method based on a spatial decomposition approach that supports dynamic load balancing for workstations containing GPUs of varying performance and memory capacity. We take advantage of high-performance features of CUDA for peer-to-peer GPU memory transfers and evaluate the performance of our algorithms on state-of-the-art GPU devices. We present parallel e ciency and performance results for simulations using multiple GPUs as system size, particle counts, and number of reactions grow. We also demonstrate multi-GPU performance in simulations of the Min protein system in E. coli . Moreover, our multi-GPU decomposition and load balancing approach can be generalized to other lattice-based problems.

Dehydration of xylose to furfural over MCM-41-supported niobium-oxide catalysts.

PubMed

García-Sancho, Cristina; Sádaba, Irantzu; Moreno-Tost, Ramón; Mérida-Robles, Josefa; Santamaría-González, José; López-Granados, Manuel; Maireles-Torres, Pedro

2013-04-01

A series of silica-based MCM-41-supported niobium-oxide catalysts are prepared, characterized by using XRD, N2 adsorption-desorption, X-ray photoelectron spectroscopy, Raman spectroscopy, and pyridine adsorption coupled to FTIR spectroscopy, and tested for the dehydration of D-xylose to furfural. Under the operating conditions used all materials are active in the dehydration of xylose to furfural (excluding the MCM-41 silica support). The xylose conversion increases with increasing Nb2 O5 content. At a loading of 16 wt % Nb2 O5 , 74.5 % conversion and a furfural yield of 36.5 % is achieved at 170 °C, after 180 min reaction time. Moreover, xylose conversion and furfural yield increase with the reaction time and temperature, attaining 82.8 and 46.2 %, respectively, at 190 °C and after 100 min reaction time. Notably, the presence of NaCl in the reaction medium further increases the furfural yield (59.9 % at 170 °C after 180 min reaction time). Moreover, catalyst reutilization is demonstrated by performing at least three runs with no loss of catalytic activity and without the requirement for an intermediate regeneration step. No significant niobium leaching is observed, and a relationship between the structure of the catalyst and the activity is proposed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Seeing diabetes: visual detection of glucose based on the intrinsic peroxidase-like activity of MoS2 nanosheets

NASA Astrophysics Data System (ADS)

Lin, Tianran; Zhong, Liangshuang; Guo, Liangqia; Fu, Fengfu; Chen, Guonan

2014-09-01

Molybdenum disulfide (MoS2) has attracted increasing research interest recently due to its unique physical, optical and electrical properties, correlated with its 2D ultrathin atomic-layered structure. Until now, however, great efforts have focused on its applications such as lithium ion batteries, transistors, and hydrogen evolution reactions. Herein, for the first time, MoS2 nanosheets are discovered to possess an intrinsic peroxidase-like activity and can catalytically oxidize 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2 to produce a color reaction. The catalytic activity follows the typical Michaelis-Menten kinetics and is dependent on temperature, pH, H2O2 concentration, and reaction time. Based on this finding, a highly sensitive and selective colorimetric method for H2O2 and glucose detection is developed and applied to detect glucose in serum samples. Moreover, a simple, inexpensive, instrument-free and portable test kit for the visual detection of glucose in normal and diabetic serum samples is constructed by utilizing agarose hydrogel as a visual detection platform.Molybdenum disulfide (MoS2) has attracted increasing research interest recently due to its unique physical, optical and electrical properties, correlated with its 2D ultrathin atomic-layered structure. Until now, however, great efforts have focused on its applications such as lithium ion batteries, transistors, and hydrogen evolution reactions. Herein, for the first time, MoS2 nanosheets are discovered to possess an intrinsic peroxidase-like activity and can catalytically oxidize 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2 to produce a color reaction. The catalytic activity follows the typical Michaelis-Menten kinetics and is dependent on temperature, pH, H2O2 concentration, and reaction time. Based on this finding, a highly sensitive and selective colorimetric method for H2O2 and glucose detection is developed and applied to detect glucose in serum samples. Moreover, a simple, inexpensive, instrument-free and portable test kit for the visual detection of glucose in normal and diabetic serum samples is constructed by utilizing agarose hydrogel as a visual detection platform. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03393k

Simulation of large-scale rule-based models

PubMed Central

Colvin, Joshua; Monine, Michael I.; Faeder, James R.; Hlavacek, William S.; Von Hoff, Daniel D.; Posner, Richard G.

2009-01-01

Motivation: Interactions of molecules, such as signaling proteins, with multiple binding sites and/or multiple sites of post-translational covalent modification can be modeled using reaction rules. Rules comprehensively, but implicitly, define the individual chemical species and reactions that molecular interactions can potentially generate. Although rules can be automatically processed to define a biochemical reaction network, the network implied by a set of rules is often too large to generate completely or to simulate using conventional procedures. To address this problem, we present DYNSTOC, a general-purpose tool for simulating rule-based models. Results: DYNSTOC implements a null-event algorithm for simulating chemical reactions in a homogenous reaction compartment. The simulation method does not require that a reaction network be specified explicitly in advance, but rather takes advantage of the availability of the reaction rules in a rule-based specification of a network to determine if a randomly selected set of molecular components participates in a reaction during a time step. DYNSTOC reads reaction rules written in the BioNetGen language which is useful for modeling protein–protein interactions involved in signal transduction. The method of DYNSTOC is closely related to that of StochSim. DYNSTOC differs from StochSim by allowing for model specification in terms of BNGL, which extends the range of protein complexes that can be considered in a model. DYNSTOC enables the simulation of rule-based models that cannot be simulated by conventional methods. We demonstrate the ability of DYNSTOC to simulate models accounting for multisite phosphorylation and multivalent binding processes that are characterized by large numbers of reactions. Availability: DYNSTOC is free for non-commercial use. The C source code, supporting documentation and example input files are available at http://public.tgen.org/dynstoc/. Contact: dynstoc@tgen.org Supplementary information: Supplementary data are available at Bioinformatics online. PMID:19213740

Synthesis and characterization of Pd-poly(N-vinyl-2-pyrrolidone)/KIT-5 nanocomposite as a polymer-inorganic hybrid catalyst for the Suzuki-Miyaura cross-coupling reaction

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

Kalbasi, Roozbeh Javad, E-mail: rkalbasi@iaush.ac.ir; Mosaddegh, Neda

2011-11-15

Composite poly(N-vinyl-2-pyrrolidone)/KIT-5 (PVP/KIT-5) was prepared by in situ polymerization method and used as a support for palladium nanoparticles obtained through the reduction of Pd(OAc){sub 2} by hydrazine hydrate. The physical and chemical properties of the catalyst were investigated by XRD, FT-IR, UV-vis, TG, BET, SEM, and TEM techniques. The catalytic performance of this novel heterogeneous catalyst was determined for the Suzuki-Miyaura cross-coupling reaction between aryl halides and phenylboronic acid in the presence of water at room temperature. The stability of the nanocomposite catalyst was excellent and could be reused 8 times without much loss of activity in the Suzuki-Miyaura cross-couplingmore » reaction. - Graphical Abstract: Pd-poly(N-vinyl-2-pyrrolidone)/KIT-5 was prepared as an organic-inorganic hybrid catalyst for the Suzuki-Miyaura reaction. The stability of the catalyst was excellent and could be reused 8 times in the Suzuki-Miyaura reaction. Highlights: > Pd-poly(N-vinyl-2-pyrrolidone)/KIT-5 was prepared as a novel nanocomposite. > Nanocomposite was prepared based on a cage-type mesoporous system. > Catalyst showed excellent activity for Suzuki-Miyaura reaction in water. > Stability of the catalyst was excellent and could be reused 8 times.« less

Reaction time and anticipatory skill of athletes in open and closed skill-dominated sport.

PubMed

Nuri, Leila; Shadmehr, Azadeh; Ghotbi, Nastaran; Attarbashi Moghadam, Behrouz

2013-01-01

In sports, reaction time and anticipatory skill are critical aspects of perceptual abilities. To date, no study has compared reaction time and anticipatory skill of athletes from open and closed skill-dominated sport. Accordingly, the present study investigated whether a difference exists in sensory-cognitive skills between these two different sport domains. Eleven volleyball players and 11 sprinters participated in this experiment. Reaction time and anticipatory skill of both groups were recorded by a custom-made software called SART (speed anticipation and reaction time test). This software consists of six sensory-cognitive tests that evaluate visual choice reaction time, visual complex choice reaction time, auditory choice reaction time, auditory complex choice reaction time, and anticipatory skill of the high speed and low speed of the ball. For each variable, an independent t-test was performed. Results suggested that sprinters were better in both auditory reaction times (P<0.001 for both tests) and volleyball players were better in both anticipatory skill tests (P = 0.007 and P = 0.04 for anticipatory skill of the high speed and low speed of the ball, respectively). However, no significant differences were found in both visual choice reaction time tests (P > 0.05 for both visual reaction time tests). It is concluded that athletes have greater sensory-cognitive skills related to their specific sport domain either open or closed.

Fuzzy logic feedback control for fed-batch enzymatic hydrolysis of lignocellulosic biomass.

PubMed

Tai, Chao; Voltan, Diego S; Keshwani, Deepak R; Meyer, George E; Kuhar, Pankaj S

2016-06-01

A fuzzy logic feedback control system was developed for process monitoring and feeding control in fed-batch enzymatic hydrolysis of a lignocellulosic biomass, dilute acid-pretreated corn stover. Digested glucose from hydrolysis reaction was assigned as input while doser feeding time and speed of pretreated biomass were responses from fuzzy logic control system. Membership functions for these three variables and rule-base were created based on batch hydrolysis data. The system response was first tested in LabVIEW environment then the performance was evaluated through real-time hydrolysis reaction. The feeding operations were determined timely by fuzzy logic control system and efficient responses were shown to plateau phases during hydrolysis. Feeding of proper amount of cellulose and maintaining solids content was well balanced. Fuzzy logic proved to be a robust and effective online feeding control tool for fed-batch enzymatic hydrolysis.

Formation, aggregation and reactivity of amorphous ferric oxyhydroxides on dissociation of Fe(III)-organic complexes in dilute aqueous suspensions

NASA Astrophysics Data System (ADS)

Bligh, Mark W.; Waite, T. David

2010-10-01

While chemical reactions that take place at the surface of amorphous ferric oxides (AFO) are known to be important in aquatic systems, incorporation of these reactions into kinetic models is hindered by a lack of ability to reliably quantify the reactivity of the surface and the changes in reactivity that occur over time. Long term decreases in the reactivity of iron oxides may be considered to result from changes in the molecular structure of the solid, however, over shorter time scales where substantial aggregation may occur, the mechanisms of reactivity loss are less clear. Precipitation of AFO may be described as a combination of homogeneous and heterogeneous reactions, however, despite its potentially significant role, the latter reaction is usually neglected in kinetic models of aquatic processes. Here, we investigate the role of AFO in scavenging dissolved inorganic ferric (Fe(III)) species (Fe') via the heterogeneous precipitation reaction during the net dissociation of organically complexed Fe(III) in seawater. Using sulfosalicylic acid (SSA) as a model ligand, AFO was shown to play a significant role in inducing the net dissociation of the Fe-SSA complexes with equations describing both the heterogeneous precipitation reaction and the aging of AFO being required to adequately describe the experimental data. An aggregation based mechanism provided a good description of AFO aging over the short time scale of the experiments. The behaviour of AFO described here has implications for the bioavailability of iron in natural systems as a result of reactions involving AFO which are recognised to occur over time scales of minutes, including adsorption of Fe' and AFO dissolution, precipitation and ageing.

Differentiating location- and distance-based processes in memory for time: an ERP study.

PubMed

Curran, Tim; Friedman, William J

2003-09-01

Memory for the time of events may benefit from reconstructive, location-based, and distance-based processes, but these processes are difficult to dissociate with behavioral methods. Neuropsychological research has emphasized the contribution of prefrontal brain mechanisms to memory for time but has not clearly differentiated location- from distance-based processing. The present experiment recorded event-related brain potentials (ERPs) while subjects completed two different temporal memory tests, designed to emphasize either location- or distance-based processing. The subjects' reports of location-based versus distance-based strategies and the reaction time pattern validated our experimental manipulation. Late (800-1,800 msec) frontal ERP effects were related to location-based processing. The results provide support for a two-process theory of memory for time and suggest that frontal memory mechanisms are specifically related to reconstructive, location-based processing.

A comparative study on visual choice reaction time for different colors in females.

PubMed

Balakrishnan, Grrishma; Uppinakudru, Gurunandan; Girwar Singh, Gaur; Bangera, Shobith; Dutt Raghavendra, Aswini; Thangavel, Dinesh

2014-01-01

Reaction time is one of the important methods to study a person's central information processing speed and coordinated peripheral movement response. Visual choice reaction time is a type of reaction time and is very important for drivers, pilots, security guards, and so forth. Previous studies were mainly on simple reaction time and there are very few studies on visual choice reaction time. The aim of our study was to compare the visual choice reaction time for red, green, and yellow colors of 60 healthy undergraduate female volunteers. After giving adequate practice, visual choice reaction time was recorded for red, green, and yellow colors using reaction time machine (RTM 608, Medicaid, Chandigarh). Repeated measures of ANOVA and Bonferroni multiple comparison were used for analysis and P < 0.05 was considered statistically significant. The results showed that both red and green had significantly less choice visual choice reaction (P values <0.0001 and 0.0002) when compared with yellow. This could be because individual color mental processing time for yellow color is more than red and green.

Ab Initio Potential Energy Surfaces and Quantum Dynamics for Polyatomic Bimolecular Reactions.

PubMed

Fu, Bina; Zhang, Dong H

2018-05-08

There has been great progress in the development of potential energy surfaces (PESs) and quantum dynamics calculations in the gas phase. The establishment of a fitting procedure for highly accurate PESs and new developments in quantum reactive scattering on reliable PESs allow accurate characterization of reaction dynamics beyond triatomic systems. This review will give the recent development in our group in constructing ab initio PESs based on neural networks and the time-dependent wave packet calculations for bimolecular reactions beyond three atoms. Bimolecular reactions of current interest to the community, namely, OH + H 2 , H + H 2 O, OH + CO, H + CH 4 , and Cl + CH 4 , are focused on. Quantum mechanical characterization of these reactions uncovers interesting dynamical phenomena with an unprecedented level of sophistication and has greatly advanced our understanding of polyatomic reaction dynamics.

The Hammett relationship and reactions in the excited electronic state: hemithioindigo Z/E-photoisomerization.

PubMed

Cordes, Thorben; Schadendorf, Torsten; Priewisch, Beate; Rück-Braun, Karola; Zinth, Wolfgang

2008-01-31

The photochemical reaction dynamics of a set of photochromic compounds based on thioindigo and stilbene molecular parts (hemithioindigos, HTI) are presented. Photochemical Z/E isomerization around the central double bond occurs with time constants of 216 ps (Z --> E) and 10 ps (E --> Z) for a 5-methyl-hemithioindigo. Chemical substitution on the stilbene moiety causes unusually strong changes in the reaction rate. Electron-donating substituents in the position para to the central double bond (e.g., para-methoxy) strongly accelerate the reaction, while the reaction is drastically slowed by electron-withdrawing groups in this position (e.g., para-nitrile). We correlate the experimental data of seven HTI-compounds in a quantitative manner using the Hammett equation and present a qualitative explanation for the application of ground-state Hammett constants to describe the photoisomerization reaction.

Colliding-Droplet Microreactor: Rapid On-Demand Inertial Mixing and Metal-Catalyzed Aqueous Phase Oxidation Processes.

PubMed

Davis, Ryan D; Jacobs, Michael I; Houle, Frances A; Wilson, Kevin R

2017-11-21

In-depth investigations of the kinetics of aqueous chemistry occurring in microdroplet environments require experimental techniques that allow a reaction to be initiated at a well-defined point in time and space. Merging microdroplets of different reactants is one such approach. The mixing dynamics of unconfined (airborne) microdroplets have yet to be studied in detail, which is an essential step toward widespread use and application of merged droplet microreactors for monitoring chemical reactions. Here, we present an on-demand experimental approach for initiating chemical reactions in and characterizing the mixing dynamics of colliding airborne microdroplets (40 ± 5 μm diameter) using a streak-based fluorescence microscopy technique. The advantages of this approach include the ability to generate two well-controlled monodisperse microdroplet streams and collide (and thus mix) the microdroplets with high spatial and temporal control while consuming small amounts of sample (<0.1 μL/s). Mixing times are influenced not only by the velocity at which microdroplets collide but also the geometry of the collision (i.e., head-on vs off-center collision). For head-on collisions, we achieve submillisecond mixing times ranging from ∼900 μs at a collision velocity of 0.1 m/s to <200 μs at ∼6 m/s. For low-velocity (<1 m/s) off-center collisions, mixing times were consistent with the head-on cases. For high-velocity (i.e., > 1 m/s) off-center collisions, mixing times increased by as much as a factor of 6 (e.g., at ∼6 m/s, mixing times increased from <200 μs for head-on collisions to ∼1200 μs for highly off-center collisions). At collision velocities >7 m/s, droplet separation and fragmentation occurred, resulting in incomplete mixing. These results suggest a limited range of collision velocities over which complete and rapid mixing can be achieved when using airborne merged microdroplets to, e.g., study reaction kinetics when reaction times are short relative to typical bulk reactor mixing times. We benchmark our reactor using an aqueous-phase oxidation reaction: iron-catalyzed hydroxyl radical production from hydrogen peroxide (Fenton's reaction) and subsequent aqueous-phase oxidation of organic species in solution. Kinetic simulations of our measurements show that quantitative agreement can be obtained using known bulk-phase kinetics for bimolecular reactions in our colliding-droplet microreactor.

Fe3O4@MOF core-shell magnetic microspheres as excellent catalysts for the Claisen-Schmidt condensation reaction

NASA Astrophysics Data System (ADS)

Ke, Fei; Qiu, Ling-Guang; Zhu, Junfa

2014-01-01

Separation and recycling of catalysts after catalytic reactions are critically required to reduce the cost of catalysts as well as to avoid the generation of waste in industrial applications. In this work, we present a facile fabrication and characterization of a novel type of MOF-based porous catalyst, namely, Fe3O4@MIL-100(Fe) core-shell magnetic microspheres. It has been shown that these catalysts not only exhibit high catalytic activities for the Claisen-Schmidt condensation reactions under environmentally friendly conditions, but remarkably, they can be easily separated and recycled without significant loss of catalytic efficiency after being used for many times. Therefore, compared to other reported catalysts used in the Claisen-Schmidt condensation reactions, these catalysts are green, cheap and more suitable for large scale industrial applications.Separation and recycling of catalysts after catalytic reactions are critically required to reduce the cost of catalysts as well as to avoid the generation of waste in industrial applications. In this work, we present a facile fabrication and characterization of a novel type of MOF-based porous catalyst, namely, Fe3O4@MIL-100(Fe) core-shell magnetic microspheres. It has been shown that these catalysts not only exhibit high catalytic activities for the Claisen-Schmidt condensation reactions under environmentally friendly conditions, but remarkably, they can be easily separated and recycled without significant loss of catalytic efficiency after being used for many times. Therefore, compared to other reported catalysts used in the Claisen-Schmidt condensation reactions, these catalysts are green, cheap and more suitable for large scale industrial applications. Electronic supplementary information (ESI) available: SEM and TEM images, and GC-MS spectra for chalcones. See DOI: 10.1039/c3nr05051c

Numerical solution of the unsteady diffusion-convection-reaction equation based on improved spectral Galerkin method

NASA Astrophysics Data System (ADS)

Zhong, Jiaqi; Zeng, Cheng; Yuan, Yupeng; Zhang, Yuzhe; Zhang, Ye

2018-04-01

The aim of this paper is to present an explicit numerical algorithm based on improved spectral Galerkin method for solving the unsteady diffusion-convection-reaction equation. The principal characteristics of this approach give the explicit eigenvalues and eigenvectors based on the time-space separation method and boundary condition analysis. With the help of Fourier series and Galerkin truncation, we can obtain the finite-dimensional ordinary differential equations which facilitate the system analysis and controller design. By comparing with the finite element method, the numerical solutions are demonstrated via two examples. It is shown that the proposed method is effective.

Direct formation of element chlorides from the corresponding element oxides through microwave-assisted carbohydrochlorination reactions.

PubMed

Nordschild, Simon; Auner, Norbert

2008-01-01

A series of technically and economically important element chlorides-such as SiCl4, BCl3, AlCl3, FeCl2, PCl3 and TiCl4-was synthesized through reactions between hydrogen chloride and the corresponding element oxides in the presence of different carbon sources with microwave assistance. This process route was optimized for demonstration purposes for tetrachlorosilane formation and successfully demonstrates the broad applicability of various silicon oxide-containing minerals and materials for carbohydrochlorination. The chlorination reaction occurs at lower temperatures than with conventional heating in a tubular oven, with substantially shorter reaction times and in better yields: quantitatively in the case of tetrachlorosilane, based on the silicon content of the starting material. The experimental procedure is very simple and provides basic information about the suitability of element compounds, especially element oxides, for carbohydrochlorination. According to the general reaction sequence element oxide-->element-->element chloride used in today's technology, this one-step carbohydrochlorination with hydrogen chloride is considerably more efficient, particularly in terms of energy input and reaction times, avoiding the isolation of the pure elements required for chlorination to give the element chlorides with use of the more corrosive and toxic chlorine gas.

Dolomite dissolution rates and possible Holocene dedolomitization of water-bearing units in the Edwards aquifer, south-central Texas

USGS Publications Warehouse

Deike, R.G.

1990-01-01

Rates of dolomite dissolution can be used to test the concept, based on geomorphologic evidence, that a major part of the Edwards aquifer could have formed within the Holocene, a timeframe of approximately 10,000 years. During formation of the aquifer in the Edwards limestone (Cretaceous, Albian) of the Balcones fault zone, dolomite dissolution and porosity development were synchronous and the result of mixing-zone dedolomitization. Initiation of the mixing zone in the early Holocene (???11,000 years before present) is suggested by the maximum age of formation of major discharge sites that allowed the influx of meteoric water into brine-filled, dolomitic preaquifer units. Dedolomitization, the dissolution of dolomite and net precipitation of calcite, has left aquifer units that are calcitic, and 40 vol.% interconnected pore space. The mass of dolomite missing is obtained by comparison of stratigraphically equivalent altered and unaltered units. One dissolution rate (1.76 ?? 10-4 mmol dolomite kgH2O-1yr-1) is determined from this mass, 104yr reaction time, and a log-linear function describing the increase in mass discharge (three orders of magnitude) during aquifer formation. The second estimated dissolution rate is obtained from the mass transfer of dolomite to solution calculated from the increase in magnesium in pore fluids selected from the modern aquifer to represent a typical flowpath during aquifer formation. A reaction time of 104yr for this mass transfer yields a rate of 0.56 ?? 10-4 mmol dolomite kgH2O-1yr-1. Both of these rates are comparable to modern rates of dolomite dissolution (0.3 to 4.5 ?? 10-4 mmol dolomite kgH2O-1yr-1) calculated from measured reaction times in the Tertiary Floridan aquifer system in Florida and the Madison aquifer in the Mississippian Madison Limestone of the Northern Great Plains. Similarity of these rates to the estimated paleo-rates of dolomite dissolution supports a 104 yr reaction timeframe. The Holocene reaction time also can be compared to a series of reaction times calculated by assuming that the mass of dolomite missing from the Edwards was removed at rates observed in the Floridan and Madison aquifers. These reaction times (for complete removal of dolomite) range from 2700 to 58,500 yr and span the Pleistocene-Holocene boundary. Finally, an estimated dolomite reaction rate during dedolomitization of the Edwards aquifer based on surface area of exposed dolomite [mmol cm-2s-1 (millimoles per square centimeter per second)] may be approximated from reaction times. This rate is directly a function of the mass of dolomite removed and the surface area exposed per pore volume passing through the rock. The surface area is available from the observed dolomite rhomb size in unaltered rock. The rate of pore fluid movement is obtained from the averaged annual discharge. Rates during formation of the Edwards aquifer calculated from all reaction times range from 10-13 to 10-14 mmol dolomite cm-2s-1. These rates are faster than rates (10-18 mmol cm-2s-1), measured in the pure laboratory system, CaMg(CO3)2CO2H2O, but slower than rates determined in an alpine stream study (10-10 to 10-11 mmol cm-2s-1) where cold glacial melt water flows over dolostone. Dolomite dissolution rates from both the Edwards and other aquifers support the concept that a major part of the Edwards aquifer could have formed within the Holocene. ?? 1990.

A TaqMan-based real-time PCR assay for porcine parvovirus 4 detection and quantification in reproductive tissues of sows

USDA-ARS?s Scientific Manuscript database

Porcine parvovirus 4 (PPV4) is a DNA virus, and a member of the Parvoviridae family within the Bocavirus genera. It was recently detected in swine, but its epidemiology and pathology remain unclear. A TaqMan-based real-time polymerase chain reaction (qPCR) assay targeting a conserved region of the O...

Biomaterials for 4D stem cell culture

PubMed Central

Hilderbrand, Amber M.; Ovadia, Elisa M.; Rehmann, Matthew S.; Kharkar, Prathamesh M.; Guo, Chen; Kloxin, April M.

2017-01-01

Stem cells reside in complex three-dimensional (3D) environments within the body that change with time, promoting various cellular functions and processes such as migration and differentiation. These complex changes in the surrounding environment dictate cell fate yet, until recently, have been challenging to mimic within cell culture systems. Hydrogel-based biomaterials are well suited to mimic aspects of these in vivo environments, owing to their high water content, soft tissue-like elasticity, and often-tunable biochemical content. Further, hydrogels can be engineered to achieve changes in matrix properties over time to better mimic dynamic native microenvironments for probing and directing stem cell function and fate. This review will focus on techniques to form hydrogel-based biomaterials and modify their properties in time during cell culture using select addition reactions, cleavage reactions, or non-covalent interactions. Recent applications of these techniques for the culture of stem cells in four dimensions (i.e., in three dimensions with changes over time) also will be discussed for studying essential stem cell processes. PMID:28717344

Accurate study on the quantum dynamics of the He + HeH(+) (X1Σ+) reaction on a new ab initio potential energy surface for the lowest 1(1)A' electronic singlet state.

PubMed

Xu, Wenwu; Zhang, Peiyu

2013-02-21

A time-dependent quantum wave packet method is used to investigate the dynamics of the He + HeH(+)(X(1)Σ(+)) reaction based on a new potential energy surface [Liang et al., J. Chem. Phys.2012, 136, 094307]. The coupled channel (CC) and centrifugal-sudden (CS) reaction probabilities as well as the total integral cross sections are calculated. A comparison of the results with and without Coriolis coupling revealed that the number of K states N(K) (K is the projection of the total angular momentum J on the body-fixed z axis) significantly influences the reaction threshold. The effective potential energy profiles of each N(K) for the He + HeH(+) reaction in a collinear geometry indicate that the barrier height gradually decreased with increased N(K). The calculated time evolution of CC and CS probability density distribution over the collision energy of 0.27-0.36 eV at total angular momentum J = 50 clearly suggests a lower reaction threshold of CC probabilities. The CC cross sections are larger than the CS results within the entire energy range, demonstrating that the Coriolis coupling effect can effectively promote the He + HeH(+) reaction.

Enzyme inhibition studies by integrated Michaelis-Menten equation considering simultaneous presence of two inhibitors when one of them is a reaction product.

PubMed

Bezerra, Rui M F; Pinto, Paula A; Fraga, Irene; Dias, Albino A

2016-03-01

To determine initial velocities of enzyme catalyzed reactions without theoretical errors it is necessary to consider the use of the integrated Michaelis-Menten equation. When the reaction product is an inhibitor, this approach is particularly important. Nevertheless, kinetic studies usually involved the evaluation of other inhibitors beyond the reaction product. The occurrence of these situations emphasizes the importance of extending the integrated Michaelis-Menten equation, assuming the simultaneous presence of more than one inhibitor because reaction product is always present. This methodology is illustrated with the reaction catalyzed by alkaline phosphatase inhibited by phosphate (reaction product, inhibitor 1) and urea (inhibitor 2). The approach is explained in a step by step manner using an Excel spreadsheet (available as a template in Appendix). Curve fitting by nonlinear regression was performed with the Solver add-in (Microsoft Office Excel). Discrimination of the kinetic models was carried out based on Akaike information criterion. This work presents a methodology that can be used to develop an automated process, to discriminate in real time the inhibition type and kinetic constants as data (product vs. time) are achieved by the spectrophotometer. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Development and evaluation of epoxidized soybean oil-based polymers

NASA Astrophysics Data System (ADS)

Juangvanich, Nuanpen

Epoxidized Soybean Oil (ESO) based polymers were developed using diamine curing agents and BF3:NH2C2H5 as catalyst. Reactions involved the curing process were explored and monitored by DSC and IR analysis. Amine-epoxy addition reactions governed the main curing reaction at the temperature range of 60--235°C, and the supplementary reactions at higher temperatures were either homopolymerization or etherification reaction. In the aliphatic curing reactions, the epoxy-rich system favored the supplementary reactions at high temperature, however, ESO cured with 1,6 hexanediamine (HDA) always produced the high temperature reaction products, due to some side reactions and the high volatile nature. The curing reaction with aromatic diamines produced inherent rigidity to the cured ESO network, which decreased the high temperature reactions. The system cured with a short aromatic diamine, 1,4-phenyldiamine (PDA), produced a small extent of high temperature reaction, as well. It was believed that the long length diamine with wide separation of the two amines underwent an intermolecular cross-linking reaction, and derived better properties than the shorter diamine. A post-cure process was used to improve the final polymer properties by increasing the temperature after the initial curing reaction was quenched due to gelation. Extending the time of post-curing did not significantly improve properties of the final ESO polymers. Exposing the cured samples at 180°C for longer than 12 hours decreased the properties of the cured material, due to thermal strain generating in the network structure. To increase time efficiency, short heat cycles were performed by post-curing right after gelation, and the cured ESO polymer had tensile strength of 32 MPa, modulus 750 MPa and toughness 1.3 MPa. With the introduction of EPON 828, the mechanical properties of a new ESO polymer improved; having strength above 40 MPa, modulus great than 1,000 MPa, and Tg higher than 40°C. Finally, a rice hull particleboard was developed using the cured ESO resin as adhesive, and the board had strength comparable to the National Bureau of Standards minimum requirement for particleboard. A 35 wt % of ESO resin imparted the highest strength for the rice hull board, with a value of 15.5 MPa.

Automatic network coupling analysis for dynamical systems based on detailed kinetic models.

PubMed

Lebiedz, Dirk; Kammerer, Julia; Brandt-Pollmann, Ulrich

2005-10-01

We introduce a numerical complexity reduction method for the automatic identification and analysis of dynamic network decompositions in (bio)chemical kinetics based on error-controlled computation of a minimal model dimension represented by the number of (locally) active dynamical modes. Our algorithm exploits a generalized sensitivity analysis along state trajectories and subsequent singular value decomposition of sensitivity matrices for the identification of these dominant dynamical modes. It allows for a dynamic coupling analysis of (bio)chemical species in kinetic models that can be exploited for the piecewise computation of a minimal model on small time intervals and offers valuable functional insight into highly nonlinear reaction mechanisms and network dynamics. We present results for the identification of network decompositions in a simple oscillatory chemical reaction, time scale separation based model reduction in a Michaelis-Menten enzyme system and network decomposition of a detailed model for the oscillatory peroxidase-oxidase enzyme system.

Laser-induced plasma chemistry of the explosive RDX with various metallic nanoparticles.

PubMed

Gottfried, Jennifer L

2012-03-01

The feasibility of exploiting plasma chemistry to study the chemical reactions between metallic nanoparticles and molecular explosives such as cyclotrimethylenetrinitramine (RDX) has been demonstrated. This method, based on laser-induced breakdown spectroscopy, involves the production of nanoparticles in a laser-induced plasma and the simultaneous observation of time-resolved atomic and molecular emission characteristic of the species involved in the intermediate chemical reactions of the nanoenergetic material in the plasma. Using this method, it has been confirmed that the presence of aluminum promotes the ejection process of carbon from the intermediate products of RDX. The time evolution of species formation, the effects of laser pulse energy, and the effects of trace metal content on the chemical reactions were also studied. © 2012 Optical Society of America

Thermal decomposition of solid phase nitromethane under various heating rates and target temperatures based on ab initio molecular dynamics simulations.

PubMed

Xu, Kai; Wei, Dong-Qing; Chen, Xiang-Rong; Ji, Guang-Fu

2014-10-01

The Car-Parrinello molecular dynamics simulation was applied to study the thermal decomposition of solid phase nitromethane under gradual heating and fast annealing conditions. In gradual heating simulations, we found that, rather than C-N bond cleavage, intermolecular proton transfer is more likely to be the first reaction in the decomposition process. At high temperature, the first reaction in fast annealing simulation is intermolecular proton transfer leading to CH3NOOH and CH2NO2, whereas the initial chemical event at low temperature tends to be a unimolecular C-N bond cleavage, producing CH3 and NO2 fragments. It is the first time to date that the direct rupture of a C-N bond has been reported as the first reaction in solid phase nitromethane. In addition, the fast annealing simulations on a supercell at different temperatures are conducted to validate the effect of simulation cell size on initial reaction mechanisms. The results are in qualitative agreement with the simulations on a unit cell. By analyzing the time evolution of some molecules, we also found that the time of first water molecule formation is clearly sensitive to heating rates and target temperatures when the first reaction is an intermolecular proton transfer.

Curing behavior and reaction kinetics of binder resins for 3D-printing investigated by dielectric analysis (DEA)

NASA Astrophysics Data System (ADS)

Möginger, B.; Kehret, L.; Hausnerova, B.; Steinhaus, J.

2016-05-01

3D-Printing is an efficient method in the field of additive manufacturing. In order to optimize the properties of manufactured parts it is essential to adapt the curing behavior of the resin systems with respect to the requirements. Thus, effects of resin composition, e.g. due to different additives such as thickener and curing agents, on the curing behavior have to be known. As the resin transfers from a liquid to a solid glass the time dependent ion viscosity was measured using DEA with flat IDEX sensors. This allows for a sensitive measurement of resin changes as the ion viscosity changes two to four decades. The investigated resin systems are based on the monomers styrene and HEMA. To account for the effects of copolymerization in the calculation of the reaction kinetics it was assumed that the reaction can be considered as a homo-polymerization having a reaction order n≠1. Then the measured ion viscosity curves are fitted with the solution of the reactions kinetics - the time dependent degree of conversion (DC-function) - for times exceeding the initiation phase representing the primary curing. The measured ion viscosity curves can nicely be fitted with the DC-function and the determined fit parameters distinguish distinctly between the investigated resin compositions.

The effect of chiropractic treatment on the reaction and response times of special operation forces military personnel: study protocol for a randomized controlled trial.

PubMed

DeVocht, James W; Smith, Dean L; Long, Cynthia R; Corber, Lance; Kane, Bridget; Jones, Thomas M; Goertz, Christine M

2016-09-20

Chiropractic care is commonly used to treat musculoskeletal conditions and has been endorsed by clinical practice guidelines as being evidence-based and cost-effective for the treatment of patients with low back pain. Gaps in the literature exist regarding the physiological outcomes of chiropractic treatment. Previous pilot work has indicated the possibility of improvements in response time following the application of chiropractic treatment. However, it is unknown whether or not chiropractic treatment is able to improve reaction and response times in specific populations of interest. One such population is the U.S. military special operation forces' (SOF) personnel. This study is a randomized controlled trial of 120 asymptomatic volunteer SOF personnel. All participants are examined by a study doctor of chiropractic (DC) for eligibility prior to randomization. The participants are randomly allocated to either a treatment group receiving four treatments of chiropractic manipulative therapy (CMT) over 2 weeks or to a wait-list control group. The wait-list group does not receive any treatment but has assessments at the same time interval as the treatment group. The outcome measures are simple reaction times for dominant hand and dominant foot, choice reaction time with prompts calling for either hand or either foot, response time using Fitts' law tasks for small movements involving eye-hand coordination, and brief whole body movements using the t-wall, a commercially available product. At the first visit, all five tests are completed so that participants can familiarize themselves with the equipment and protocol. Assessments at the second and the final visits are used for data analysis. SOF personnel are highly motivated and extremely physically fit individuals whose occupation requires reaction times that are as quick as possible during the course of their assigned duties. A goal of CMT is to maximize the functionality and integration of the neuromusculoskeletal systems. Therefore, chiropractic treatment may be able to optimize the capacity of the numerous components of those systems, resulting in improved reaction time. The objective of this study is to test the hypothesis that CMT improves reaction and response times in asymptomatic SOF personnel. ClinicalTrials.gov, NCT02168153 . Registered on 12 June 2014.

Microwave assisted preparation of magnesium phosphate cement (MPC) for orthopedic applications: a novel solution to the exothermicity problem.

PubMed

Zhou, Huan; Agarwal, Anand K; Goel, Vijay K; Bhaduri, Sarit B

2013-10-01

There are two interesting features of this paper. First, we report herein a novel microwave assisted technique to prepare phosphate based orthopedic cements, which do not generate any exothermicity during setting. The exothermic reactions during the setting of phosphate cements can cause tissue damage during the administration of injectable compositions and hence a solution to the problem is sought via microwave processing. This solution through microwave exposure is based on a phenomenon that microwave irradiation can remove all water molecules from the alkaline earth phosphate cement paste to temporarily stop the setting reaction while preserving the active precursor phase in the formulation. The setting reaction can be initiated a second time by adding aqueous medium, but without any exothermicity. Second, a special emphasis is placed on using this technique to synthesize magnesium phosphate cements for orthopedic applications with their enhanced mechanical properties and possible uses as drug and protein delivery vehicles. The as-synthesized cements were evaluated for the occurrences of exothermic reactions, setting times, presence of Mg-phosphate phases, compressive strength levels, microstructural features before and after soaking in (simulated body fluid) SBF, and in vitro cytocompatibility responses. The major results show that exposure to microwaves solves the exothermicity problem, while simultaneously improving the mechanical performance of hardened cements and reducing the setting times. As expected, the cements are also found to be cytocompatible. Finally, it is observed that this process can be applied to calcium phosphate cements system (CPCs) as well. Based on the results, this microwave exposure provides a novel technique for the processing of injectable phosphate bone cement compositions. © 2013.

Fluorescence Correlation Spectroscopy and Nonlinear Stochastic Reaction-Diffusion

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

Del Razo, Mauricio; Pan, Wenxiao; Qian, Hong

2014-05-30

The currently existing theory of fluorescence correlation spectroscopy (FCS) is based on the linear fluctuation theory originally developed by Einstein, Onsager, Lax, and others as a phenomenological approach to equilibrium fluctuations in bulk solutions. For mesoscopic reaction-diffusion systems with nonlinear chemical reactions among a small number of molecules, a situation often encountered in single-cell biochemistry, it is expected that FCS time correlation functions of a reaction-diffusion system can deviate from the classic results of Elson and Magde [Biopolymers (1974) 13:1-27]. We first discuss this nonlinear effect for reaction systems without diffusion. For nonlinear stochastic reaction-diffusion systems there are no closedmore » solutions; therefore, stochastic Monte-Carlo simulations are carried out. We show that the deviation is small for a simple bimolecular reaction; the most significant deviations occur when the number of molecules is small and of the same order. Extending Delbrück-Gillespie’s theory for stochastic nonlinear reactions with rapidly stirring to reaction-diffusion systems provides a mesoscopic model for chemical and biochemical reactions at nanometric and mesoscopic level such as a single biological cell.« less

Synthesis and spectroscopic characterization of azoic dyes based on pyrazolone derivatives catalyzed by an acidic ionic liquid supported on silica-coated magnetite nanoparticle

NASA Astrophysics Data System (ADS)

Isaad, Jalal; El Achari, Ahmida

2018-02-01

Novel family of azoic dyes pyrazolone based were prepared by an efficient and rapid methodology through diazotization reaction of different pyrazolone amine derivatives, in the presence of acidic ionic liquid supported on silica-coated magnetite nanoparticles as acidic catalyst at room temperature and under solvent-free conditions. The attractive advantages of the present process include short reaction times, milder and cleaner conditions, higher purity and yields, easy isolation of products, easier work-up procedure and lower generation of waste or pollution. This catalyst was easily separated by an external magnet and the recovered catalyst was reused several times without any significant loss of activity. Therefore, this method provides improved protocol over the existing methods.

Mineral trioxide aggregate-based sealer: analysis of tissue reactions to a new endodontic material.

PubMed

Scarparo, Roberta Kochenborger; Haddad, Daniel; Acasigua, Gerson Arison Xavier; Fossati, Anna Cristina Medeiros; Fachin, Elaine Vianna Freitas; Grecca, Fabiana Soares

2010-07-01

The aim of this study was to evaluate the subcutaneous connective tissue reaction to mineral trioxide aggregate (MTA)-based sealer (Endo CPM Sealer; CPM Sealer; EGEO SRL, Buenos Aires, Argentina), MTA, and an epoxy resin-based sealer (AH Plus; Dentsply HERO Indústria e Comércio Ltda, Petrópolis, RJ, Brazil). Polyethylene tubes containing the test materials and empty tubes (control group) were implanted in the subcutaneous tissue of 18 rats. After 7, 30, and 60 days, observations were made for cellular inflammatory components, fibrous condensation, and abscess formation. Comparisons between groups and periods of time were made using the Friedman test and the Kruskall-Wallis test. Lymphocytes and plasmacytes were more intensely observed in the reaction to AH Plus sealer after 30 days (p < 0.05). MTA and the Endo CPM Sealer presented a behavior similar to that of the control group throughout the whole experiment. The Endo CPM Sealer presented biological potential. Characteristics of the inflammatory reaction were equivalent to those produced by MTA. Copyright 2010 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

How Mood and Task Complexity Affect Children's Recognition of Others’ Emotions

PubMed Central

Cummings, Andrew J.; Rennels, Jennifer L.

2013-01-01

Previous studies examined how mood affects children's accuracy in matching emotional expressions and labels (label-based tasks). This study was the first to assess how induced mood (positive, neutral, or negative) influenced 5- to 8-year-olds’ accuracy and reaction time using both context-based tasks, which required inferring a character's emotion from a vignette, and label-based tasks. Both tasks required choosing one of four facial expressions to respond. Children responded more accurately to label-based questions relative to context-based questions at 5 to 7 years of age, but showed no differences at 8 years of age, and when the emotional expression being identified was happiness, sadness, or surprise, but not disgust. For the context-based questions, children were more accurate at inferring sad and disgusted emotions compared to happy and surprised emotions. Induced positive mood facilitated 5-year-olds’ processing (decreased reaction time) in both tasks compared to induced negative and neutral moods. Results demonstrate how task type and children's mood influence children's emotion processing at different ages. PMID:24489442

Enhancement of force patterns classification based on Gaussian distributions.

PubMed

Ertelt, Thomas; Solomonovs, Ilja; Gronwald, Thomas

2018-01-23

Description of the patterns of ground reaction force is a standard method in areas such as medicine, biomechanics and robotics. The fundamental parameter is the time course of the force, which is classified visually in particular in the field of clinical diagnostics. Here, the knowledge and experience of the diagnostician is relevant for its assessment. For an objective and valid discrimination of the ground reaction force pattern, a generic method, especially in the medical field, is absolutely necessary to describe the qualities of the time-course. The aim of the presented method was to combine the approaches of two existing procedures from the fields of machine learning and the Gauss approximation in order to take advantages of both methods for the classification of ground reaction force patterns. The current limitations of both methods could be eliminated by an overarching method. Twenty-nine male athletes from different sports were examined. Each participant was given the task of performing a one-legged stopping maneuver on a force plate from the maximum possible starting speed. The individual time course of the ground reaction force of each subject was registered and approximated on the basis of eight Gaussian distributions. The descriptive coefficients were then classified using Bayesian regulated neural networks. The different sports served as the distinguishing feature. Although the athletes were all given the same task, all sports referred to a different quality in the time course of ground reaction force. Meanwhile within each sport, the athletes were homogeneous. With an overall prediction (R = 0.938) all subjects/sports were classified correctly with 94.29% accuracy. The combination of the two methods: the mathematical description of the time course of ground reaction forces on the basis of Gaussian distributions and their classification by means of Bayesian regulated neural networks, seems an adequate and promising method to discriminate the ground reaction forces without any loss of information. Copyright © 2017 Elsevier Ltd. All rights reserved.

Use of Ambient Ionization High-Resolution Mass Spectrometry for the Kinetic Analysis of Organic Surface Reactions.

PubMed

Sen, Rickdeb; Escorihuela, Jorge; Smulders, Maarten M J; Zuilhof, Han

2016-04-12

In contrast to homogeneous systems, studying the kinetics of organic reactions on solid surfaces remains a difficult task due to the limited availability of appropriate analysis techniques that are general, high-throughput, and capable of offering quantitative, structural surface information. Here, we demonstrate how direct analysis in real time mass spectrometry (DART-MS) complies with above considerations and can be used for determining interfacial kinetic parameters. The presented approach is based on the use of a MS tag that--in principle--allows application to other reactions. To show the potential of DART-MS, we selected the widely applied strain-promoted alkyne-azide cycloaddition (SPAAC) as a model reaction to elucidate the effects of the nanoenvironment on the interfacial reaction rate.

The Effect of Lateral Ankle Ligament Repair in Muscle Reaction Time in Patients with Mechanical Ankle Instability.

PubMed

Li, H-Y; Zheng, J-J; Zhang, J; Hua, Y-H; Chen, S-Y

2015-11-01

Studies have shown that functional ankle instability can result in prolonged muscle reaction time. However, the deficit in muscle reaction time in patients with mechanical ankle instability (MAI) and the effect of lateral ankle ligament repair on muscle reaction time are unclear. The purpose of this study was to identify the deficit in muscle reaction time, and to evaluate the role of lateral ligament repair in improving muscle reaction time in MAI patients. Sixteen MAI patients diagnosed with lateral ankle ligament tears by ultrasonography and magnetic resonance imaging underwent arthroscopic debridement and open lateral ankle ligament repair with a modified Broström procedure. One day before the operation, reaction times of the tibialis anterior and peroneus longus muscles were recorded following sudden inversion perturbation while walking on a custom walkway, and anterior drawer test (ADT) and American Orthopaedic Foot and Ankle Society (AOFAS) scale score were evaluated. Six months postoperatively, muscle reaction time, ADT and AOFAS scale score were reevaluated, and muscle reaction times in 15 healthy controls were also recorded. Preoperatively, the affected ankles in the MAI group had significantly delayed tibialis anterior and peroneus longus muscles reaction times compared with controls. Six months after the operation, median AOFAS scale scores were significantly greater than preoperatively, and ADT was negative in the MAI group. However, the affected ankles in the MAI group showed no difference in muscle reaction time compared with preoperative values. MAI patients had prolonged muscle reaction time. The modified Broström procedure produced satisfactory clinical outcomes in MAI patients, but did not shorten reaction times of the tibialis anterior and peroneus longus muscles. © Georg Thieme Verlag KG Stuttgart · New York.

An asymptotic induced numerical method for the convection-diffusion-reaction equation

NASA Technical Reports Server (NTRS)

Scroggs, Jeffrey S.; Sorensen, Danny C.

1988-01-01

A parallel algorithm for the efficient solution of a time dependent reaction convection diffusion equation with small parameter on the diffusion term is presented. The method is based on a domain decomposition that is dictated by singular perturbation analysis. The analysis is used to determine regions where certain reduced equations may be solved in place of the full equation. Parallelism is evident at two levels. Domain decomposition provides parallelism at the highest level, and within each domain there is ample opportunity to exploit parallelism. Run time results demonstrate the viability of the method.

Self-consistent collective coordinate for reaction path and inertial mass

NASA Astrophysics Data System (ADS)

Wen, Kai; Nakatsukasa, Takashi

2016-11-01

We propose a numerical method to determine the optimal collective reaction path for a nucleus-nucleus collision, based on the adiabatic self-consistent collective coordinate (ASCC) method. We use an iterative method, combining the imaginary-time evolution and the finite amplitude method, for the solution of the ASCC coupled equations. It is applied to the simplest case, α -α scattering. We determine the collective path, the potential, and the inertial mass. The results are compared with other methods, such as the constrained Hartree-Fock method, Inglis's cranking formula, and the adiabatic time-dependent Hartree-Fock (ATDHF) method.

Computational methods for diffusion-influenced biochemical reactions.

PubMed

Dobrzynski, Maciej; Rodríguez, Jordi Vidal; Kaandorp, Jaap A; Blom, Joke G

2007-08-01

We compare stochastic computational methods accounting for space and discrete nature of reactants in biochemical systems. Implementations based on Brownian dynamics (BD) and the reaction-diffusion master equation are applied to a simplified gene expression model and to a signal transduction pathway in Escherichia coli. In the regime where the number of molecules is small and reactions are diffusion-limited predicted fluctuations in the product number vary between the methods, while the average is the same. Computational approaches at the level of the reaction-diffusion master equation compute the same fluctuations as the reference result obtained from the particle-based method if the size of the sub-volumes is comparable to the diameter of reactants. Using numerical simulations of reversible binding of a pair of molecules we argue that the disagreement in predicted fluctuations is due to different modeling of inter-arrival times between reaction events. Simulations for a more complex biological study show that the different approaches lead to different results due to modeling issues. Finally, we present the physical assumptions behind the mesoscopic models for the reaction-diffusion systems. Input files for the simulations and the source code of GMP can be found under the following address: http://www.cwi.nl/projects/sic/bioinformatics2007/

Co-solvent effects on reaction rate and reaction equilibrium of an enzymatic peptide hydrolysis.

PubMed

Wangler, A; Canales, R; Held, C; Luong, T Q; Winter, R; Zaitsau, D H; Verevkin, S P; Sadowski, G

2018-04-25

This work presents an approach that expresses the Michaelis constant KaM and the equilibrium constant Kth of an enzymatic peptide hydrolysis based on thermodynamic activities instead of concentrations. This provides KaM and Kth values that are independent of any co-solvent. To this end, the hydrolysis reaction of N-succinyl-l-phenylalanine-p-nitroanilide catalysed by the enzyme α-chymotrypsin was studied in pure buffer and in the presence of the co-solvents dimethyl sulfoxide, trimethylamine-N-oxide, urea, and two salts. A strong influence of the co-solvents on the measured Michaelis constant (KM) and equilibrium constant (Kx) was observed, which was found to be caused by molecular interactions expressed as activity coefficients. Substrate and product activity coefficients were used to calculate the activity-based values KaM and Kth for the co-solvent free reaction. Based on these constants, the co-solvent effect on KM and Kx was predicted in almost quantitative agreement with the experimental data. The approach presented here does not only reveal the importance of understanding the thermodynamic non-ideality of reactions taking place in biological solutions and in many technological applications, it also provides a framework for interpreting and quantifying the multifaceted co-solvent effects on enzyme-catalysed reactions that are known and have been observed experimentally for a long time.

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

Martinez-Guerra, Edith; Gude, Veera Gnaneswar, E-mail: gude@cee.msstate.edu

Highlights: • Pulse sonication effect on transesterification of waste vegetable oil was studied. • Effects of ethanol, methanol, and alcohol mixtures on FAMEs yield were evaluated. • Effect of ultrasonic intensity, power density, and its output rates were evaluated. • Alcohol mixtures resulted in higher biodiesel yields due to better solubility. - Abstract: This study reports on the effects of direct pulse sonication and the type of alcohol (methanol and ethanol) on the transesterification reaction of waste vegetable oil without any external heating or mechanical mixing. Biodiesel yields and optimum process conditions for the transesterification reaction involving ethanol, methanol, andmore » ethanol–methanol mixtures were evaluated. The effects of ultrasonic power densities (by varying sample volumes), power output rates (in W), and ultrasonic intensities (by varying the reactor size) were studied for transesterification reaction with ethanol, methanol and ethanol–methanol (50%-50%) mixtures. The optimum process conditions for ethanol or methanol based transesterification reaction of waste vegetable oil were determined as: 9:1 alcohol to oil ratio, 1% wt. catalyst amount, 1–2 min reaction time at a power output rate between 75 and 150 W. It was shown that the transesterification reactions using ethanol–methanol mixtures resulted in biodiesel yields as high as >99% at lower power density and ultrasound intensity when compared to ethanol or methanol based transesterification reactions.« less

Supercritical water oxidation of landfill leachate

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

Wang Shuzhong, E-mail: s_z_wang@yahoo.cn; Guo Yang; Chen Chongming

2011-09-15

Highlights: > Thermal analysis of NH{sub 3} in supercritical water oxidation reaction. > Research on the catalytic reaction of landfill leachate by using response surface method. > Kinetic research of supercritical water oxidation of NH{sub 3} with and without MnO{sub 2} catalyst. - Abstract: In this paper, ammonia as an important ingredient in landfill leachate was mainly studied. Based on Peng-Robinson formulations and Gibbs free energy minimization method, the estimation of equilibrium composition and thermodynamic analysis for supercritical water oxidation of ammonia (SCWO) was made. As equilibrium is reached, ammonia could be totally oxidized in SCW. N{sub 2} is themore » main product, and the formation of NO{sub 2} and NO could be neglected. The investigation on SCWO of landfill leachate was conducted in a batch reactor at temperature of 380-500 deg. C, reaction time of 50-300 s and pressure of 25 MPa. The effect of reaction parameters such as oxidant equivalent ratio, reaction time and temperature were investigated. The results showed that COD and NH{sub 3} conversion improved as temperature, reaction time and oxygen excess increased. Compared to organics, NH{sub 3} is a refractory compound in supercritical water. The conversion of COD and NH{sub 3} were higher in the presence of MnO{sub 2} than that without catalyst. The interaction between reaction temperature and time was analyzed by using response surface method (RSM) and the results showed that its influence on the NH{sub 3} conversion was relatively insignificant in the case without catalyst. A global power-law rate expression was regressed from experimental data to estimate the reaction rate of NH{sub 3}. The activation energy with and without catalyst for NH{sub 3} oxidation were 107.07 {+-} 8.57 kJ/mol and 83.22 {+-} 15.62 kJ/mol, respectively.« less

A fluorescence-based centrifugal microfluidic system for parallel detection of multiple allergens

NASA Astrophysics Data System (ADS)

Chen, Q. L.; Ho, H. P.; Cheung, K. L.; Kong, S. K.; Suen, Y. K.; Kwan, Y. W.; Li, W. J.; Wong, C. K.

2010-02-01

This paper reports a robust polymer based centrifugal microfluidic analysis system that can provide parallel detection of multiple allergens in vitro. Many commercial food products (milk, bean, pollen, etc.) may introduce allergy to people. A low-cost device for rapid detection of allergens is highly desirable. With this as the objective, we have studied the feasibility of using a rotating disk device incorporating centrifugal microfluidics for performing actuationfree and multi-analyte detection of different allergen species with minimum sample usage and fast response time. Degranulation in basophils or mast cells is an indicator to demonstrate allergic reaction. In this connection, we used acridine orange (AO) to demonstrate degranulation in KU812 human basophils. It was found that the AO was released from granules when cells were stimulated by ionomycin, thus signifying the release of histamine which accounts for allergy symptoms [1-2]. Within this rotating optical platform, major microfluidic components including sample reservoirs, reaction chambers, microchannel and flow-control compartments are integrated into a single bio-compatible polydimethylsiloxane (PDMS) substrate. The flow sequence and reaction time can be controlled precisely. Sequentially through varying the spinning speed, the disk may perform a variety of steps on sample loading, reaction and detection. Our work demonstrates the feasibility of using centrifugation as a possible immunoassay system in the future.

Subnanosecond measurements of detonation fronts in solid high explosives

NASA Astrophysics Data System (ADS)

Sheffield, S. A.; Bloomquist, D. D.; Tarver, C. M.

1984-04-01

Detonation fronts in solid high explosives have been examined through measurements of particle velocity histories resulting from the interaction of a detonation wave with a thin metal foil backed by a water window. Using a high time resolution velocity-interferometer system, experiments were conducted on three explosives—a TATB (1,3,5-triamino-trinitrobenzene)-based explosive called PBX-9502, TNT (2,4,6-Trinitrotoluene), and CP (2-{5-cyanotetrazolato} pentaamminecobalt {III} perchlorate). In all cases, detonation-front rise times were found to be less than the 300 ps resolution of the interferometer system. The thermodynamic state in the front of the detonation wave was estimated to be near the unreacted state determined from an extrapolation of low-pressure unreacted Hugoniot data for both TNT and PBX-9502 explosives. Computer calculations based on an ignition and growth model of a Zeldovich-von Neumann-Doering (ZND) detonation wave show good agreement with the measurements. By using the unreacted Hugoniot and a JWL equation of state for the reaction products, we estimated the initial reaction rate in the high explosive after the detonation wave front interacted with the foil to be 40 μs-1 for CP, 60 μs-1 for TNT, and 80 μs-1 for PBX-9502. The shape of the profiles indicates the reaction rate decreases as reaction proceeds.

A Radiation Chemistry Code Based on the Greens Functions of the Diffusion Equation

NASA Technical Reports Server (NTRS)

Plante, Ianik; Wu, Honglu

2014-01-01

Ionizing radiation produces several radiolytic species such as.OH, e-aq, and H. when interacting with biological matter. Following their creation, radiolytic species diffuse and chemically react with biological molecules such as DNA. Despite years of research, many questions on the DNA damage by ionizing radiation remains, notably on the indirect effect, i.e. the damage resulting from the reactions of the radiolytic species with DNA. To simulate DNA damage by ionizing radiation, we are developing a step-by-step radiation chemistry code that is based on the Green's functions of the diffusion equation (GFDE), which is able to follow the trajectories of all particles and their reactions with time. In the recent years, simulations based on the GFDE have been used extensively in biochemistry, notably to simulate biochemical networks in time and space and are often used as the "gold standard" to validate diffusion-reaction theories. The exact GFDE for partially diffusion-controlled reactions is difficult to use because of its complex form. Therefore, the radial Green's function, which is much simpler, is often used. Hence, much effort has been devoted to the sampling of the radial Green's functions, for which we have developed a sampling algorithm This algorithm only yields the inter-particle distance vector length after a time step; the sampling of the deviation angle of the inter-particle vector is not taken into consideration. In this work, we show that the radial distribution is predicted by the exact radial Green's function. We also use a technique developed by Clifford et al. to generate the inter-particle vector deviation angles, knowing the inter-particle vector length before and after a time step. The results are compared with those predicted by the exact GFDE and by the analytical angular functions for free diffusion. This first step in the creation of the radiation chemistry code should help the understanding of the contribution of the indirect effect in the formation of DNA damage and double-strand breaks.

Optimization of extraction of chitin from procambarus clarkia shell by Box-Behnken design

NASA Astrophysics Data System (ADS)

Dong, Fang; Qiu, Hailong; Jia, Shaoqian; Dai, Cuiping; Kong, Qingxin; Xu, Changliang

2018-06-01

This paper investigated the optimizing extraction processing of chitin from procambarus clarkia shell by Box-Behnken design. Firstly, four independent variables were explored in single factor experiments, namely, concentration of hydrochloric acid, soaking time, concentration of sodium hydroxide and reaction time. Then, based on the results of the above experiments, four factors and three levels experiments were planned by Box-Behnken design. According to the experimental results, we harvested a second-order polynomial equation using multiple regression analysis. In addition, the optimum extraction process of chitin of the model was obtained: concentration of HCl solution 1.54mol/L, soaking time 19.87h, concentration of NaOH solution 2.9mol/L and reaction time 3.54h. For proving the accuracy of the model, we finished the verification experiment under the following conditions: concentration of hydrochloric acid 1.5mol/L, soaking time 20h, concentration of sodium hydroxide 3mol/L and reaction time 3.5h. The actual yield of chitin reached 18.76%, which was very close to the predicted yield (18.66%) of the model. The result indicated that the optimum extraction processing of chitin was feasible and practical.

Exciplex mediated photoinduced electron transfer reactions of phthalocyanine-fullerene dyads.

PubMed

Niemi, Marja; Tkachenko, Nikolai V; Efimov, Alexander; Lehtivuori, Heli; Ohkubo, Kei; Fukuzumi, Shunichi; Lemmetyinen, Helge

2008-07-31

Evidences of an intramolecular exciplex intermediate in a photoinduced electron transfer (ET) reaction of double-linked free-base and zinc phthalocyanine-C60 dyads were found. This was the first time for a dyad with phthalocyanine donor. Excitation of the phthalocyanine moiety of the dyads results in rapid ET from phthalocyanine to fullerene via an exciplex state in both polar and nonpolar solvents. Relaxation of the charge-separated (CS) state Pc(*+)-C60(*-) in a polar solvent occurs directly to the ground state in 30-70 ps. In a nonpolar solvent, roughly 20% of the molecules undergo transition from the CS state to phthalocyanine triplet state (3)Pc*-C60 before relaxation to the ground state. Formation of the CS state was confirmed with electron spin resonance measurements at low temperature in both polar and nonpolar solvent. Reaction schemes for the photoinduced ET reactions of the dyads were completed with rate constants obtained from the time-resolved absorption and emission measurements and with state energies obtained from the fluorescence, phosphorescence, and voltammetric measurements.

Alkaline in situ transesterification of Aurantiochytrium sp. KRS 101 using potassium carbonate.

PubMed

Sung, Mina; Han, Jong-In

2016-04-01

The aims of this work were to evaluate K2CO3 as a potent alkaline catalyst for in situ transesterification of Aurantiochytrium sp. KRS 101, one step process in which oil extraction and conversion take place together. This K2CO3-based in situ transesterification was optimized in terms of recovery yield of fatty acid methyl esters (FAMEs) by way of varying biomass concentration, reaction temperature, reaction time, and catalyst concentration. The optimal condition was achieved at 50g/L of biomass concentration and 1% of K2CO3 in the methanol, 25°C of reaction temperature, and 5min of reaction time, resulting in the FAME recovery yield over 90%. It was found that K2CO3 performed better than any other tested catalysts including acids, supporting the notion that K2CO3 is a promising catalyst, especially for in situ transesterification. Copyright © 2016. Published by Elsevier Ltd.

Electrokinetic Microstrirring to Enhance Immunoassays

NASA Astrophysics Data System (ADS)

Feldman, Hope; Sigurdson, Marin; Meinhart, Carl

2006-11-01

Electrokinetic microstirring is used to improve the sensitivity of microfluidic heterogeneous immuno-sensors by enhancing the transport in diffusion-limited reactions. The AC electrokinetic force, Electrothermal Flow, is exploited to create a circular stirring fluid motion, thereby providing more binding opportunities between suspended and wall-immobilized molecules. This process can significantly reduce test times, important for both field-portable biosensors and for lab-based assays. A 2-D numerical simulation model is used to predict the effect of electrothermal flow on a heterogeneous immunoassay resulting from an AC potential applied to two parallel electrodes. The binding is increased by a factor of 7 for an applied voltage of 10 Vrms. The effect was investigated experimentally using a high affinity biotin-streptavidin reaction. Microstirred reaction rates were compared with passive reactions. The measurements show on average an order of magnitude increase in binding between immobilized biotin and fluorescently-labeled streptavidin after 5 minutes. Therefore, this technique shows significant promise for reducing incubation time and enhancing the sensitivity of immunoassays.

Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction.

PubMed

He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

2016-08-09

The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.

Generic approach to access barriers in dehydrogenation reactions

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

Yu, Liang; Vilella, Laia; Abild-Pedersen, Frank

The introduction of linear energy correlations, which explicitly relate adsorption energies of reaction intermediates and activation energies in heterogeneous catalysis, has proven to be a key component in the computational search for new and promising catalysts. A simple linear approach to estimate activation energies still requires a significant computational effort. To simplify this process and at the same time incorporate the need for enhanced complexity of reaction intermediates, we generalize a recently proposed approach that evaluates transition state energies based entirely on bond-order conservation arguments. Here, we show that similar variation of the local electronic structure along the reaction coordinatemore » introduces a set of general functions that accurately defines the transition state energy and are transferable to other reactions with similar bonding nature. With such an approach, more complex reaction intermediates can be targeted with an insignificant increase in computational effort and without loss of accuracy.« less

Generic approach to access barriers in dehydrogenation reactions

DOE PAGES

Yu, Liang; Vilella, Laia; Abild-Pedersen, Frank

2018-03-08

The introduction of linear energy correlations, which explicitly relate adsorption energies of reaction intermediates and activation energies in heterogeneous catalysis, has proven to be a key component in the computational search for new and promising catalysts. A simple linear approach to estimate activation energies still requires a significant computational effort. To simplify this process and at the same time incorporate the need for enhanced complexity of reaction intermediates, we generalize a recently proposed approach that evaluates transition state energies based entirely on bond-order conservation arguments. Here, we show that similar variation of the local electronic structure along the reaction coordinatemore » introduces a set of general functions that accurately defines the transition state energy and are transferable to other reactions with similar bonding nature. With such an approach, more complex reaction intermediates can be targeted with an insignificant increase in computational effort and without loss of accuracy.« less

Time-Resolved and Operando XAS Studies on Heterogeneous Catalysts - From the Gas Phase Towards Reactions in Supercritical Fluids

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

Grunwaldt, Jan-Dierk; Baiker, Alfons

2007-02-02

x-ray absorption spectroscopy is a well-suited technique to uncover the structure of heterogeneous catalysts under reaction conditions. Different aspects of in situ cell design suitable for dynamic and catalytic studies are discussed. In addition, criteria are presented that allow estimating the influence external and internal mass transfer. Starting with studies on gas-solid reactions, including structure-activity relationships, this concept is extended to liquid-solid reactions, reactions at high pressure and in supercritical fluids. The following examples are discussed in more detail: partial oxidation of methane over Pt-Rh/Al2O3, reduction of a Cu/ZnO catalyst, alcohol oxidation over Bi-promoted Pd/Al2O3 in liquid phase and overmore » Pd/Al2O3 in supercritical CO2, and batch reactions (e.g. CO2-fixation over zinc-based catalysts)« less

CaFeAl mixed oxide derived heterogeneous catalysts for transesterification of soybean oil to biodiesel.

PubMed

Lu, Yongsheng; Zhang, Zaiwu; Xu, Yunfeng; Liu, Qiang; Qian, Guangren

2015-08-01

CaAl layered double oxides (LDO) were prepared by co-precipitation and calcined at 750°C, and then applied to biodiesel production by transesterification reaction between methanol and soybean oil. Compared with characteristics of CaFe/LDO and CaAl/LDO, CaFeAl/LDO had the best performance based on prominent catalytic activity and stability, and achieved over 90% biodiesel yield, which stayed stable (over 85%) even after 8 cycles of reaction. The optimal catalytic reaction condition was 12:1M-ratio of methanol/oil, reaction temperatures of 60°C, 270rpm stirring rate, 60min reaction time, and 6% weight-ratio of catalyst/oil. In addition, the CaFeAl/LDO catalyst is insoluble in both methanol and methyl esters and can be easily separated for further reaction, turning it into an excellent alternative for biodiesel synthesis. Copyright © 2015 Elsevier Ltd. All rights reserved.

Rapid solid-state metathesis route to transition-metal doped titanias

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

Coleman, Nathaniel; Perera, Sujith; Gillan, Edward G., E-mail: edward-gillan@uiowa.edu

2015-12-15

Rapid solid-state metathesis (SSM) reactions are often short-lived highly exothermic reactions that yield a molten alkali halide salt that aids in product growth and crystallization. SSM reactions may also produce kinetically stabilized structures due to the short (seconds) reaction times. This report describes the investigation of rapid SSM reactions in the synthesis of transition-metal doped titanias (M–TiO{sub 2}). The dopant targeted compositions were ten mol percent and based on elemental analysis, many of the M–TiO{sub 2} samples were close to this targeted level. Based on surface analysis, some samples showed large enrichment in surface dopant content, particularly chromium and manganesemore » doped samples. Due to the highly exothermic nature of these reactions, rutile structured TiO{sub 2} was observed in all cases. The M–TiO{sub 2} samples are visible colored and show magnetic and optical properties consistent with the dopant in an oxide environment. UV and visible photocatalytic experiments with these visibly colored rutile M–TiO{sub 2} powders showed that many of them are strongly absorbent for methylene blue dye and degrade the dye under both UV and visible light illumination. This work may open up SSM reactions as an alternate non-thermodynamic reaction strategy for dopant incorporation into a wide range of oxide and non-oxides.« less

Accurate prediction of severe allergic reactions by a small set of environmental parameters (NDVI, temperature).

PubMed

Notas, George; Bariotakis, Michail; Kalogrias, Vaios; Andrianaki, Maria; Azariadis, Kalliopi; Kampouri, Errika; Theodoropoulou, Katerina; Lavrentaki, Katerina; Kastrinakis, Stelios; Kampa, Marilena; Agouridakis, Panagiotis; Pirintsos, Stergios; Castanas, Elias

2015-01-01

Severe allergic reactions of unknown etiology,necessitating a hospital visit, have an important impact in the life of affected individuals and impose a major economic burden to societies. The prediction of clinically severe allergic reactions would be of great importance, but current attempts have been limited by the lack of a well-founded applicable methodology and the wide spatiotemporal distribution of allergic reactions. The valid prediction of severe allergies (and especially those needing hospital treatment) in a region, could alert health authorities and implicated individuals to take appropriate preemptive measures. In the present report we have collecterd visits for serious allergic reactions of unknown etiology from two major hospitals in the island of Crete, for two distinct time periods (validation and test sets). We have used the Normalized Difference Vegetation Index (NDVI), a satellite-based, freely available measurement, which is an indicator of live green vegetation at a given geographic area, and a set of meteorological data to develop a model capable of describing and predicting severe allergic reaction frequency. Our analysis has retained NDVI and temperature as accurate identifiers and predictors of increased hospital severe allergic reactions visits. Our approach may contribute towards the development of satellite-based modules, for the prediction of severe allergic reactions in specific, well-defined geographical areas. It could also probably be used for the prediction of other environment related diseases and conditions.

Accurate Prediction of Severe Allergic Reactions by a Small Set of Environmental Parameters (NDVI, Temperature)

PubMed Central

Andrianaki, Maria; Azariadis, Kalliopi; Kampouri, Errika; Theodoropoulou, Katerina; Lavrentaki, Katerina; Kastrinakis, Stelios; Kampa, Marilena; Agouridakis, Panagiotis; Pirintsos, Stergios; Castanas, Elias

2015-01-01

Severe allergic reactions of unknown etiology,necessitating a hospital visit, have an important impact in the life of affected individuals and impose a major economic burden to societies. The prediction of clinically severe allergic reactions would be of great importance, but current attempts have been limited by the lack of a well-founded applicable methodology and the wide spatiotemporal distribution of allergic reactions. The valid prediction of severe allergies (and especially those needing hospital treatment) in a region, could alert health authorities and implicated individuals to take appropriate preemptive measures. In the present report we have collecterd visits for serious allergic reactions of unknown etiology from two major hospitals in the island of Crete, for two distinct time periods (validation and test sets). We have used the Normalized Difference Vegetation Index (NDVI), a satellite-based, freely available measurement, which is an indicator of live green vegetation at a given geographic area, and a set of meteorological data to develop a model capable of describing and predicting severe allergic reaction frequency. Our analysis has retained NDVI and temperature as accurate identifiers and predictors of increased hospital severe allergic reactions visits. Our approach may contribute towards the development of satellite-based modules, for the prediction of severe allergic reactions in specific, well-defined geographical areas. It could also probably be used for the prediction of other environment related diseases and conditions. PMID:25794106

Exercise and Cognitive Functioning in People With Chronic Whiplash-Associated Disorders: A Controlled Laboratory Study.

PubMed

Ickmans, Kelly; Meeus, Mira; De Kooning, Margot; De Backer, Annabelle; Kooremans, Daniëlle; Hubloue, Ives; Schmitz, Tom; Van Loo, Michel; Nijs, Jo

2016-02-01

Controlled laboratory study. In addition to persistent pain, people with chronic whiplash-associated disorders (WAD) commonly deal with cognitive dysfunctions. In healthy individuals, aerobic exercise has a positive effect on cognitive performance, and preliminary evidence in other chronic pain conditions reveals promising results as well. However, there is evidence that people with chronic WAD may show a worsening of the symptom complex following physical exertion. To examine postexercise cognitive performance in people with chronic WAD. People with chronic WAD (n = 27) and healthy, inactive, sex- and age-matched controls (n = 27) performed a single bout of an incremental submaximal cycling exercise. Before and after the exercise, participants completed 2 performance-based cognitive tests assessing selective and sustained attention, cognitive inhibition, and simple and choice reaction time. At baseline, people with chronic WAD displayed significantly lower scores on sustained attention and simple reaction time (P<.001), but not on selective attention, cognitive inhibition, and choice reaction time (P>.05), compared with healthy controls. Postexercise, both groups showed significantly improved selective attention and choice reaction time (chronic WAD, P = .001; control, P<.001), while simple reaction time significantly increased (P = .037) only in the control group. In both groups, no other significant changes in sustained attention, cognitive inhibition, pain, and fatigue were observed (P>.05). In the short term, postexercise cognitive functioning, pain, and fatigue were not aggravated in people with chronic WAD. However, randomized controlled trials are required to study the longer-term and isolated effects of exercise on cognitive functioning.

Enhanced photovoltaic performance of dye sensitized solar cell using SnO2 nanoflowers

NASA Astrophysics Data System (ADS)

Arote, Sandeep A.; Tabhane, Vilas A.; Pathan, Habib M.

2018-01-01

The study highlighted enhanced performance of SnO2 based DSSC using photoanode with nanostructured morphology. The simple organic surfactant free hydrothermal synthesis method was used for preparation of SnO2 nanoflowers for dye sensitized solar cell (DSSC) application. The hydrothermal reaction time was varied to obtain different SnO2 nanostructures. The hydrothermal reaction time showed considerable effect on optical and structural properties of the prepared samples. The results indicated that the prepared samples were pure rutile SnO2. The band gap of prepared samples was greater than bulk SnO2 and varied from 3.64 to 3.81 eV with increase in hydrothermal reaction time. With increase in reaction time from 4 to 24 h, the microstructure of SnO2 changed from agglomerated nanoparticles to nanopetals and finally to self-assembled nanoflowers. Flower-like SnO2 nanostructures showed size around 300-700 nm, and composed of large numbers of 3 dimensional petals connected with each other forming 3D nanoflowers by self-assembly. Consequently, the DSSC with flower-like SnO2 nanostructures exhibited good photovoltaic performance with Voc, Jsc and η about 0.43 V, 4.36 mA/cm2 and 1.11%, respectively.

Reaction Time and Joint Kinematics During Functional Movement in Recently Concussed Individuals.

PubMed

Lynall, Robert C; Blackburn, J Troy; Guskiewicz, Kevin M; Marshall, Stephen W; Plummer, Prudence; Mihalik, Jason P

2018-05-01

To compare movement reaction time and joint kinematics between athletes with recent concussion and matched control recreational athletes during 3 functional tasks. Cross-sectional. Laboratory. College-aged recreational athletes (N=30) comprising 2 groups (15 participants each): (1) recent concussion group (median time since concussion, 126d; range, 28-432d) and (2) age- and sex-matched control group with no recent concussions. We investigated movement reaction time and joint kinematics during 3 tasks: (1) jump landing, (2) anticipated cut, and (3) unanticipated cut. Reaction time and reaction time cost (jump landing reaction time-cut reaction time/jump landing reaction time×100%), along with trunk, hip, and knee joint angles in the sagittal and frontal planes at initial ground contact. There were no reaction time between-group differences, but the control group displayed improved reaction time cost (10.7%) during anticipated cutting compared with the concussed group (0.8%; P=.030). The control group displayed less trunk flexion than the concussed group during the nondominant anticipated cut (5.1° difference; P=.022). There were no other kinematic between-group differences (P≥.079). We observed subtle reaction time and kinematic differences between individuals with recent concussion and those without concussion more than a month after return to activity after concussion. The clinical interpretation of these findings remains unclear, but may have future implications for postconcussion management and rehabilitation. Copyright © 2018 American Congress of Rehabilitation Medicine. Published by Elsevier Inc. All rights reserved.

(1)H NMR-based DS determination of barley starch sulfates prepared in 1-allyl-3-methylimidazolium chloride.

PubMed

Kärkkäinen, Johanna; Wik, Tiia-Riikka; Niemelä, Matti; Lappalainen, Katja; Joensuu, Päivi; Lajunen, Marja

2016-01-20

The use of natural resources in a development of products and materials is currently increasing. Starch is one of the investigated resources due to its bioavailability, biodegradability, safety and affordability. In this study, native barley starch was sulfated using a SO3-pyridine complex. The reaction was carried out for the first time using 1-allyl-3-methylimidazolium chloride ionic liquid, an excellent solvent for the starch modification. Reaction conditions (temperature, time and amount of the reagent) were studied using an experimental design. Starch sulfates with the degree of substitution (DS) 1.37 were obtained when the reaction was carried out at 40 °C for 75 min with 4:1 molar ratio of SO3-pyridine complex:anhydroglucose unit. The determination of DS was based on (1)H NMR instead of elemental analysis, which showed overestimated DS values in this study. Starch sulfates were analyzed with FTIR and HPLC, which showed that products contained small and large sulfated molecules. Copyright © 2015 Elsevier Ltd. All rights reserved.

Reduction Reaction Activity on Pt-Monolayer-Shell PdIr/Ni-core Catalysts

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

Song, Liang; Vukmirovic, Miomir B.; Adzic, Radoslav R.

Platinum monolayer oxygen reduction reaction catalysts present promising way of reducing the Pt content without scarifying its fuel cell performance. We present a facile way of preparing Pt monolayer shell PdIr-based core catalysts, which showed much higher activity for oxygen reduction reaction than that of TKK 46.6% Pt/C catalyst. Among tested samples, PtMLPd2Ir/Ni/C performs the best with Pt and Platinum Group Metal mass activity around 9 and 0.25 times higher of that of TKK 46.6% Pt/C. In addition, accelerated aging test indicates its excellent durability.

Reduction Reaction Activity on Pt-Monolayer-Shell PdIr/Ni-core Catalysts

DOE PAGES

Song, Liang; Vukmirovic, Miomir B.; Adzic, Radoslav R.

2018-05-14

Platinum monolayer oxygen reduction reaction catalysts present promising way of reducing the Pt content without scarifying its fuel cell performance. We present a facile way of preparing Pt monolayer shell PdIr-based core catalysts, which showed much higher activity for oxygen reduction reaction than that of TKK 46.6% Pt/C catalyst. Among tested samples, PtMLPd2Ir/Ni/C performs the best with Pt and Platinum Group Metal mass activity around 9 and 0.25 times higher of that of TKK 46.6% Pt/C. In addition, accelerated aging test indicates its excellent durability.

Time dependent three-dimensional body frame quantal wave packet treatment of the H + H2 exchange reaction on the Liu-Siegbahn-Truhlar-Horowitz (LSTH) surface

NASA Technical Reports Server (NTRS)

Neuhauser, Daniel; Baer, Michael; Judson, Richard S.; Kouri, Donald J.

1989-01-01

The first successful application of the three-dimensional quantum body frame wave packet approach to reactive scattering is reported for the H + H2 exchange reaction on the LSTH potential surface. The method used is based on a procedure for calculating total reaction probabilities from wave packets. It is found that converged, vibrationally resolved reactive probabilities can be calculated with a grid that is not much larger than required for the pure inelastic calculation. Tabular results are presented for several energies.

Non-invasive estimation of dissipation from non-equilibrium fluctuations in chemical reactions.

PubMed

Muy, S; Kundu, A; Lacoste, D

2013-09-28

We show how to extract an estimate of the entropy production from a sufficiently long time series of stationary fluctuations of chemical reactions. This method, which is based on recent work on fluctuation theorems, is direct, non-invasive, does not require any knowledge about the underlying dynamics and is applicable even when only partial information is available. We apply it to simple stochastic models of chemical reactions involving a finite number of states, and for this case, we study how the estimate of dissipation is affected by the degree of coarse-graining present in the input data.

Localized temperature and chemical reaction control in nanoscale space by nanowire array.

PubMed

Jin, C Yan; Li, Zhiyong; Williams, R Stanley; Lee, K-Cheol; Park, Inkyu

2011-11-09

We introduce a novel method for chemical reaction control with nanoscale spatial resolution based on localized heating by using a well-aligned nanowire array. Numerical and experimental analysis shows that each individual nanowire could be selectively and rapidly Joule heated for local and ultrafast temperature modulation in nanoscale space (e.g., maximum temperature gradient 2.2 K/nm at the nanowire edge; heating/cooling time < 2 μs). By taking advantage of this capability, several nanoscale chemical reactions such as polymer decomposition/cross-linking and direct and localized hydrothermal synthesis of metal oxide nanowires were demonstrated.

A Paper-Based Device for Performing Loop-Mediated Isothermal Amplification with Real-Time Simultaneous Detection of Multiple DNA Targets.

PubMed

Seok, Youngung; Joung, Hyou-Arm; Byun, Ju-Young; Jeon, Hyo-Sung; Shin, Su Jeong; Kim, Sanghyo; Shin, Young-Beom; Han, Hyung Soo; Kim, Min-Gon

2017-01-01

Paper-based diagnostic devices have many advantages as a one of the multiple diagnostic test platforms for point-of-care (POC) testing because they have simplicity, portability, and cost-effectiveness. However, despite high sensitivity and specificity of nucleic acid testing (NAT), the development of NAT based on a paper platform has not progressed as much as the others because various specific conditions for nucleic acid amplification reactions such as pH, buffer components, and temperature, inhibitions from technical differences of paper-based device. Here, we propose a paper-based device for performing loop-mediated isothermal amplification (LAMP) with real-time simultaneous detection of multiple DNA targets. We determined the optimal chemical components to enable dry conditions for the LAMP reaction without lyophilization or other techniques. We also devised the simple paper device structure by sequentially stacking functional layers, and employed a newly discovered property of hydroxynaphthol blue fluorescence to analyze real-time LAMP signals in the paper device. This proposed platform allowed analysis of three different meningitis DNA samples in a single device with single-step operation. This LAMP-based multiple diagnostic device has potential for real-time analysis with quantitative detection of 10 2 -10 5 copies of genomic DNA. Furthermore, we propose the transformation of DNA amplification devices to a simple and affordable paper system approach with great potential for realizing a paper-based NAT system for POC testing.

A Paper-Based Device for Performing Loop-Mediated Isothermal Amplification with Real-Time Simultaneous Detection of Multiple DNA Targets

PubMed Central

Seok, Youngung; Joung, Hyou-Arm; Byun, Ju-Young; Jeon, Hyo-Sung; Shin, Su Jeong; Kim, Sanghyo; Shin, Young-Beom; Han, Hyung Soo; Kim, Min-Gon

2017-01-01

Paper-based diagnostic devices have many advantages as a one of the multiple diagnostic test platforms for point-of-care (POC) testing because they have simplicity, portability, and cost-effectiveness. However, despite high sensitivity and specificity of nucleic acid testing (NAT), the development of NAT based on a paper platform has not progressed as much as the others because various specific conditions for nucleic acid amplification reactions such as pH, buffer components, and temperature, inhibitions from technical differences of paper-based device. Here, we propose a paper-based device for performing loop-mediated isothermal amplification (LAMP) with real-time simultaneous detection of multiple DNA targets. We determined the optimal chemical components to enable dry conditions for the LAMP reaction without lyophilization or other techniques. We also devised the simple paper device structure by sequentially stacking functional layers, and employed a newly discovered property of hydroxynaphthol blue fluorescence to analyze real-time LAMP signals in the paper device. This proposed platform allowed analysis of three different meningitis DNA samples in a single device with single-step operation. This LAMP-based multiple diagnostic device has potential for real-time analysis with quantitative detection of 102-105 copies of genomic DNA. Furthermore, we propose the transformation of DNA amplification devices to a simple and affordable paper system approach with great potential for realizing a paper-based NAT system for POC testing. PMID:28740546

Hydrothermal carbonization of food waste for nutrient recovery and reuse.

PubMed

Idowu, Ifeolu; Li, Liang; Flora, Joseph R V; Pellechia, Perry J; Darko, Samuel A; Ro, Kyoung S; Berge, Nicole D

2017-11-01

Food waste represents a rather large and currently underutilized source of potentially available and reusable nutrients. Laboratory-scale experiments evaluating the hydrothermal carbonization of food wastes collected from restaurants were conducted to understand how changes in feedstock composition and carbonization process conditions influence primary and secondary nutrient fate. Results from this work indicate that at all evaluated reaction times and temperatures, the majority of nitrogen, calcium, and magnesium remain integrated within the solid-phase, while the majority of potassium and sodium reside in the liquid-phase. The fate of phosphorus is dependent on reaction times and temperatures, with solid-phase integration increasing with higher reaction temperature and longer time. A series of leaching experiments to determine potential solid-phase nutrient availability were also conducted and indicate that, at least in the short term, nitrogen release from the solids is small, while almost all of the phosphorus present in the solids produced from carbonizing at 225 and 250°C is released. At a reaction temperature of 275°C, smaller fractions of the solid-phase total phosphorus are released as reaction times increase, likely due to increased solids incorporation. Using these data, it is estimated that up to 0.96% and 2.30% of nitrogen and phosphorus-based fertilizers, respectively, in the US can be replaced by the nutrients integrated within hydrochar and liquid-phases generated from the carbonization of currently landfilled food wastes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of Reaction Time and Temperature on Chemical, Structural, Optical, and Photoelectrical Properties of PbS Thin Films Chemically Deposited from the Pb(OAc)2-NaOH-TU-TEA Aqueous System

NASA Astrophysics Data System (ADS)

Castelo-González, O. A.; Sotelo-Lerma, M.; García-Valenzuela, J. A.

2017-01-01

Lead sulfide (PbS) thin films have been deposited on float glass substrates by the chemical bath deposition technique using a Pb(CH3COO)2-NaOH-(NH2)2CS-N(CH2CH2OH)3 definite aqueous system. The chemical and structural characteristics, as well as the variation of the optical and photoelectrical properties, were studied as functions of reaction time and temperature. For this purpose, the following characterization techniques were employed: x-ray diffraction analysis, x-ray photoelectron spectroscopy, ultraviolet-visible-near infrared spectrophotometry, and dark and light current measurements. Based on the results, it was observed that increase in the reaction temperature increased the deposition rate of the PbS thin film (associated with the cubic crystalline structure); increase of this parameter from 40°C to 70°C (with reaction time of 60 min) led to an increase of the thickness from ˜129 nm to ˜459 nm and the crystallite size ( D) from 15.3 nm to 20.2 nm; on the other hand, increase in temperature decreased the energy bandgap ( E g) from 1.66 eV to 0.51 eV and the relative photosensitivity factor ( S ph) from 0.468 to 0.032. A similar effect was obtained with increase of the reaction time for given temperature.

Decontamination of chemical tracers in droplets by a submerging thin film flow

NASA Astrophysics Data System (ADS)

Landel, Julien R.; McEvoy, Harry; Dalziel, Stuart B.

2016-11-01

We investigate the decontamination of chemical tracers contained in small viscous drops by a submerging falling film. This problem has applications in the decontamination of hazardous chemicals, following accidental releases or terrorist attacks. Toxic droplets lying on surfaces are cleaned by spraying a liquid decontaminant over the surface. The decontaminant film submerges the droplets, without detaching them, in order to neutralize toxic chemicals in the droplets. The decontamination process is controlled by advection, diffusion and reaction processes near the drop-film interface. Chemical tracers dissolve into the film flow forming a thin diffusive boundary layer at the interface. The chemical tracers are then neutralized through a reaction with a chemical decontaminant transported in the film. We assume in this work that the decontamination process occurs mainly in the film phase owing to low solubility of the decontaminant in the drop phase. We analyze the impact of the reaction time scale, assuming first-order reaction, in relation with the characteristic advection and diffusion time scales in the case of a single droplet. Using theoretical, numerical and experimental means, we find that the reaction time scale need to be significantly smaller than the characteristic time scale in the diffusive boundary layer in order to enhance noticeably the decontamination of a single toxic droplet. We discuss these results in the more general case of the decontamination of a large number of droplets. This material is based upon work supported by the Defense Threat Reduction Agency under Contract No. HDTRA1-12-D-0003-0001.

Genetic and environmental contributions to the associations between intraindividual variability in reaction time and cognitive function.

PubMed

Finkel, Deborah; Pedersen, Nancy L

2014-01-01

Intraindividual variability (IIV) in reaction time has been related to cognitive decline, but questions remain about the nature of this relationship. Mean and range in movement and decision time for simple reaction time were available from 241 individuals aged 51-86 years at the fifth testing wave of the Swedish Adoption/Twin Study of Aging. Cognitive performance on four factors was also available: verbal, spatial, memory, and speed. Analyses indicated that range in reaction time could be used as an indicator of IIV. Heritability estimates were 35% for mean reaction and 20% for range in reaction. Multivariate analysis indicated that the genetic variance on the memory, speed, and spatial factors is shared with genetic variance for mean or range in reaction time. IIV shares significant genetic variance with fluid ability in late adulthood, over and above and genetic variance shared with mean reaction time.

The influenced of reaction time on the degradation of palm oil empty fruit bunch (EFB) in hydrothermal carbonization

NASA Astrophysics Data System (ADS)

Sarwono, Rakhman; Kurniawan, Hendris Hendarsyah

2017-11-01

Hydrothermal carbonization (HTC) of empty fruit bunch (EFB) of palm oil in different reaction times were investigated. Experiments were carried out in an autoclave at different reaction time of 3,6,9, 15, 20, 25 and 40 hours. With a fixed solid/liquid ratio of 5 gram of EFB in 50 ml water as a solvent, and temperature reaction of 250 °C. Increase the reaction time the soluble products are also increased. The liquid products were analyzed using GCMS to determine the chemical composition. The chemical composition were greatly affected by the reaction time. The main component was glycolic acid, by increasing the reaction time made the varieties of chemical compositions in liquid products, especially for the glycolic acid component, it was decreased slightly. The higher heating value (HHV) also increase slighly by increasing the reaction time both solid and liquid products.

Inattention and Reaction Time Variability Are Linked to Ventromedial Prefrontal Volume in Adolescents.

PubMed

Albaugh, Matthew D; Orr, Catherine; Chaarani, Bader; Althoff, Robert R; Allgaier, Nicholas; D'Alberto, Nicholas; Hudson, Kelsey; Mackey, Scott; Spechler, Philip A; Banaschewski, Tobias; Brühl, Rüdiger; Bokde, Arun L W; Bromberg, Uli; Büchel, Christian; Cattrell, Anna; Conrod, Patricia J; Desrivières, Sylvane; Flor, Herta; Frouin, Vincent; Gallinat, Jürgen; Goodman, Robert; Gowland, Penny; Grimmer, Yvonne; Heinz, Andreas; Kappel, Viola; Martinot, Jean-Luc; Paillère Martinot, Marie-Laure; Nees, Frauke; Orfanos, Dimitri Papadopoulos; Penttila, Jani; Poustka, Luise; Paus, Tomáš; Smolka, Michael N; Struve, Maren; Walter, Henrik; Whelan, Robert; Schumann, Gunter; Garavan, Hugh; Potter, Alexandra S

2017-11-01

Neuroimaging studies of attention-deficit/hyperactivity disorder (ADHD) have most commonly reported volumetric abnormalities in the basal ganglia, cerebellum, and prefrontal cortices. Few studies have examined the relationship between ADHD symptomatology and brain structure in population-based samples. We investigated the relationship between dimensional measures of ADHD symptomatology, brain structure, and reaction time variability-an index of lapses in attention. We also tested for associations between brain structural correlates of ADHD symptomatology and maps of dopaminergic gene expression. Psychopathology and imaging data were available for 1538 youths. Parent ratings of ADHD symptoms were obtained using the Development and Well-Being Assessment and the Strengths and Difficulties Questionnaire (SDQ). Self-reports of ADHD symptoms were assessed using the youth version of the SDQ. Reaction time variability was available in a subset of participants. For each measure, whole-brain voxelwise regressions with gray matter volume were calculated. Parent ratings of ADHD symptoms (Development and Well-Being Assessment and SDQ), adolescent self-reports of ADHD symptoms on the SDQ, and reaction time variability were each negatively associated with gray matter volume in an overlapping region of the ventromedial prefrontal cortex. Maps of DRD1 and DRD2 gene expression were associated with brain structural correlates of ADHD symptomatology. This is the first study to reveal relationships between ventromedial prefrontal cortex structure and multi-informant measures of ADHD symptoms in a large population-based sample of adolescents. Our results indicate that ventromedial prefrontal cortex structure is a biomarker for ADHD symptomatology. These findings extend previous research implicating the default mode network and dopaminergic dysfunction in ADHD. Copyright © 2017 Society of Biological Psychiatry. Published by Elsevier Inc. All rights reserved.

Pilot Test of a Novel Method for Assessing Community Response to Low-Amplitude Sonic Booms

NASA Technical Reports Server (NTRS)

Fidell, Sanford; Horonjeff, Richard D.; Harris, Michael

2012-01-01

A pilot test of a novel method for assessing residents annoyance to sonic booms was performed. During a two-week period, residents of the base housing area at Edwards Air Force Base provided data on their reactions to sonic booms using Smartphone-based interviews. Noise measurements were conducted at the same time. The report presents information about data collection methods and about test participants reactions to low-amplitude sonic booms. The latter information should not be viewed as definitive for several reasons. It may not be reliably generalized to the wider U.S. residential population (because it was not derived from a representative random sample) and the sample itself was not large.

Water nanoelectrolysis: A simple model

NASA Astrophysics Data System (ADS)

Olives, Juan; Hammadi, Zoubida; Morin, Roger; Lapena, Laurent

2017-12-01

A simple model of water nanoelectrolysis—defined as the nanolocalization at a single point of any electrolysis phenomenon—is presented. It is based on the electron tunneling assisted by the electric field through the thin film of water molecules (˜0.3 nm thick) at the surface of a tip-shaped nanoelectrode (micrometric to nanometric curvature radius at the apex). By applying, e.g., an electric potential V1 during a finite time t1, and then the potential -V1 during the same time t1, we show that there are three distinct regions in the plane (t1, V1): one for the nanolocalization (at the apex of the nanoelectrode) of the electrolysis oxidation reaction, the second one for the nanolocalization of the reduction reaction, and the third one for the nanolocalization of the production of bubbles. These parameters t1 and V1 completely control the time at which the electrolysis reaction (of oxidation or reduction) begins, the duration of this reaction, the electrolysis current intensity (i.e., the tunneling current), the number of produced O2 or H2 molecules, and the radius of the nanolocalized bubbles. The model is in good agreement with our experiments.

A mathematical model for foreign body reactions in 2D.

PubMed

Su, Jianzhong; Gonzales, Humberto Perez; Todorov, Michail; Kojouharov, Hristo; Tang, Liping

2011-02-01

The foreign body reactions are commonly referred to the network of immune and inflammatory reactions of human or animals to foreign objects placed in tissues. They are basic biological processes, and are also highly relevant to bioengineering applications in implants, as fibrotic tissue formations surrounding medical implants have been found to substantially reduce the effectiveness of devices. Despite of intensive research on determining the mechanisms governing such complex responses, few mechanistic mathematical models have been developed to study such foreign body reactions. This study focuses on a kinetics-based predictive tool in order to analyze outcomes of multiple interactive complex reactions of various cells/proteins and biochemical processes and to understand transient behavior during the entire period (up to several months). A computational model in two spatial dimensions is constructed to investigate the time dynamics as well as spatial variation of foreign body reaction kinetics. The simulation results have been consistent with experimental data and the model can facilitate quantitative insights for study of foreign body reaction process in general.

Time-Resolved Kinetic Chirped-Pulse Rotational Spectroscopy in a Room-Temperature Flow Reactor

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

Zaleski, Daniel P.; Harding, Lawrence B.; Klippenstein, Stephen J.

Chirped-pulse Fourier transform millimeter-wave spectroscopy is a potentially powerful tool for studying chemical reaction dynamics and kinetics. Branching ratios of multiple reaction products and intermediates can be measured with unprecedented chemical specificity; molecular isomers, conformers, and vibrational states have distinct rotational spectra. Here we demonstrate chirped-pulse spectroscopy of vinyl cyanide photoproducts in a flow tube reactor at ambient temperature of 295 K and pressures of 1-10 mu bar. This in situ and time-resolved experiment illustrates the utility of this novel approach to investigating chemical reaction dynamics and kinetics. Following 193 nm photodissociation of CH2CHCN, we observe rotational relaxation of energizedmore » HCN, HNC, and HCCCN photoproducts with 10 mu s time resolution and sample the vibrational population distribution of HCCCN. The experimental branching ratio HCN/HCCCN is compared with a model based on RRKM theory using high-level ab initio calculations, which were in turn validated by comparisons to Active Thermochemical Tables enthalpies.« less

Reaction time inconsistency in a spatial stroop task: age-related differences through childhood and adulthood.

PubMed

Williams, Benjamin R; Strauss, Esther H; Hultsch, David F; Hunter, Michael A

2007-07-01

Age-related differences in inconsistency of reaction time (RT) across the life span were examined on a task with differing levels of demand on executive control. A total of 546 participants, aged 5 to 76 years, completed a spatial Stroop task that permitted observations under three conditions (congruent, incongruent, and neutral) according to the correspondence between the required response (based on stimulus direction) and stimulus location. An interference effect was observed across all ages. Analyses of neutral condition data replicated previous research demonstrating RT inconsistency follows a U-shaped developmental curve across the life span. The relationship between age and inconsistency, however, depended on condition: inconsistency in the congruent condition was higher than inconsistency in both the neutral and incongruent conditions across middle-aged groups. Reaction time inconsistency may reflect processing efficiency that is maximal in young adulthood and may also be sensitive to fluctuations in performance that reflect momentarily highly efficient responding.

Time-Resolved Kinetic Chirped-Pulse Rotational Spectroscopy in a Room-Temperature Flow Reactor

DOE PAGES

Zaleski, Daniel P.; Harding, Lawrence B.; Klippenstein, Stephen J.; ...

2017-12-01

Chirped-pulse Fourier transform millimeter-wave spectroscopy is a potentially powerful tool for studying chemical reaction dynamics and kinetics. Branching ratios of multiple reaction products and intermediates can be measured with unprecedented chemical specificity; molecular isomers, conformers, and vibrational states have distinct rotational spectra. Here we demonstrate chirped-pulse spectroscopy of vinyl cyanide photoproducts in a flow tube reactor at ambient temperature of 295 K and pressures of 1-10 mu bar. This in situ and time-resolved experiment illustrates the utility of this novel approach to investigating chemical reaction dynamics and kinetics. Following 193 nm photodissociation of CH2CHCN, we observe rotational relaxation of energizedmore » HCN, HNC, and HCCCN photoproducts with 10 mu s time resolution and sample the vibrational population distribution of HCCCN. The experimental branching ratio HCN/HCCCN is compared with a model based on RRKM theory using high-level ab initio calculations, which were in turn validated by comparisons to Active Thermochemical Tables enthalpies.« less

Micromixer-based time-resolved NMR: applications to ubiquitin protein conformation.

PubMed

Kakuta, Masaya; Jayawickrama, Dimuthu A; Wolters, Andrew M; Manz, Andreas; Sweedler, Jonathan V

2003-02-15

Time-resolved NMR spectroscopy is used to studychanges in protein conformation based on the elapsed time after a change in the solvent composition of a protein solution. The use of a micromixer and a continuous-flow method is described where the contents of two capillary flows are mixed rapidly, and then the NMR spectra of the combined flow are recorded at precise time points. The distance after mixing the two fluids and flow rates define the solvent-protein interaction time; this method allows the measurement of NMR spectra at precise mixing time points independent of spectral acquisition time. Integration of a micromixer and a microcoil NMR probe enables low-microliter volumes to be used without losing significant sensitivity in the NMR measurement. Ubiquitin, the model compound, changes its conformation from native to A-state at low pH and in 40% or higher methanol/water solvents. Proton NMR resonances of the His-68 and the Tyr-59 of ubiquitin are used to probe the conformational changes. Mixing ubiquitin and methanol solutions under low pH at microliter per minute flow rates yields both native and A-states. As the flow rate decreases, yielding longer reaction times, the population of the A-state increases. The micromixer-NMR system can probe reaction kinetics on a time scale of seconds.

Salience-Based Selection: Attentional Capture by Distractors Less Salient Than the Target

PubMed Central

Goschy, Harriet; Müller, Hermann Joseph

2013-01-01

Current accounts of attentional capture predict the most salient stimulus to be invariably selected first. However, existing salience and visual search models assume noise in the map computation or selection process. Consequently, they predict the first selection to be stochastically dependent on salience, implying that attention could even be captured first by the second most salient (instead of the most salient) stimulus in the field. Yet, capture by less salient distractors has not been reported and salience-based selection accounts claim that the distractor has to be more salient in order to capture attention. We tested this prediction using an empirical and modeling approach of the visual search distractor paradigm. For the empirical part, we manipulated salience of target and distractor parametrically and measured reaction time interference when a distractor was present compared to absent. Reaction time interference was strongly correlated with distractor salience relative to the target. Moreover, even distractors less salient than the target captured attention, as measured by reaction time interference and oculomotor capture. In the modeling part, we simulated first selection in the distractor paradigm using behavioral measures of salience and considering the time course of selection including noise. We were able to replicate the result pattern we obtained in the empirical part. We conclude that each salience value follows a specific selection time distribution and attentional capture occurs when the selection time distributions of target and distractor overlap. Hence, selection is stochastic in nature and attentional capture occurs with a certain probability depending on relative salience. PMID:23382820

Study on the Increased Probability of Detecting Adverse Drug Reactions Based on Bayes' Theorem: Evaluation of the Usefulness of Information on the Onset Timing of Adverse Drug Reactions.

PubMed

Oshima, Shinji; Enjuji, Takako; Negishi, Akio; Akimoto, Hayato; Ohara, Kousuke; Okita, Mitsuyoshi; Numajiri, Sachihiko; Inoue, Naoko; Ohshima, Shigeru; Terao, Akira; Kobayashi, Daisuke

2017-09-01

In order to avoid adverse drug reactions (ADRs), pharmacists are reconstructing ADR-related information based on various types of data gathered from patients, and then providing this information to patients. Among the data provided to patients is the time-to-onset of ADRs after starting the medication (i.e., ADR onset timing information). However, a quantitative evaluation of the effect of onset timing information offered by pharmacists on the probability of ADRs occurring in patients receiving this information has not been reported to date. In this study, we extracted 40 ADR-drug combinations from the data in the Japanese Adverse Drug Event Report database. By applying Bayes' theorem to these combinations, we quantitatively evaluated the usefulness of onset timing information as an ADR detection predictor. As a result, when information on days after taking medication was added, 54 ADR-drug combinations showed a likelihood ratio (LR) in excess of 2. In particular, when considering the ADR-drug combination of anaphylactic shock with levofloxacin or loxoprofen, the number of days elapsed between start of medication and the onset of the ADR was 0, which corresponded to increased likelihood ratios (LRs) of 138.7301 or 58.4516, respectively. When information from 1-7 d after starting medication was added to the combination of liver disorder and acetaminophen, the LR was 11.1775. The results of this study indicate the clinical usefulness of offering information on ADR onset timing.

Enhanced DNA Sensing via Catalytic Aggregation of Gold Nanoparticles

PubMed Central

Huttanus, Herbert M.; Graugnard, Elton; Yurke, Bernard; Knowlton, William B.; Kuang, Wan; Hughes, William L.; Lee, Jeunghoon

2014-01-01

A catalytic colorimetric detection scheme that incorporates a DNA-based hybridization chain reaction into gold nanoparticles was designed and tested. While direct aggregation forms an inter-particle linkage from only ones target DNA strand, the catalytic aggregation forms multiple linkages from a single target DNA strand. Gold nanoparticles were functionalized with thiol-modified DNA strands capable of undergoing hybridization chain reactions. The changes in their absorption spectra were measured at different times and target concentrations and compared against direct aggregation. Catalytic aggregation showed a multifold increase in sensitivity at low target concentrations when compared to direct aggregation. Gel electrophoresis was performed to compare DNA hybridization reactions in catalytic and direct aggregation schemes, and the product formation was confirmed in the catalytic aggregation scheme at low levels of target concentrations. The catalytic aggregation scheme also showed high target specificity. This application of a DNA reaction network to gold nanoparticle-based colorimetric detection enables highly-sensitive, field-deployable, colorimetric readout systems capable of detecting a variety of biomolecules. PMID:23891867

Writing and compiling code into biochemistry.

PubMed

Shea, Adam; Fett, Brian; Riedel, Marc D; Parhi, Keshab

2010-01-01

This paper presents a methodology for translating iterative arithmetic computation, specified as high-level programming constructs, into biochemical reactions. From an input/output specification, we generate biochemical reactions that produce output quantities of proteins as a function of input quantities performing operations such as addition, subtraction, and scalar multiplication. Iterative constructs such as "while" loops and "for" loops are implemented by transferring quantities between protein types, based on a clocking mechanism. Synthesis first is performed at a conceptual level, in terms of abstract biochemical reactions - a task analogous to high-level program compilation. Then the results are mapped onto specific biochemical reactions selected from libraries - a task analogous to machine language compilation. We demonstrate our approach through the compilation of a variety of standard iterative functions: multiplication, exponentiation, discrete logarithms, raising to a power, and linear transforms on time series. The designs are validated through transient stochastic simulation of the chemical kinetics. We are exploring DNA-based computation via strand displacement as a possible experimental chassis.

Flavylium network of chemical reactions in confined media: modulation of 3',4',7-trihydroxyflavilium reactions by host-guest interactions with cucurbit[7]uril.

PubMed

Basílio, Nuno; Pina, Fernando

2014-08-04

In moderately acidic aqueous solutions, flavylium compounds undergo a pH-, and in some cases, light-dependent array of reversible chemical reactions. This network can be described as a single acid-base reaction involving a flavylium cation (acidic form) and a mixture of basic forms (quinoidal base, hemiketal and cis and trans chalcones). The apparent pK'a of the system and the relative mole fractions of the basic forms can be modulated by the interaction with cucurbit[7]uril. The system is studied by using (1) H NMR spectroscopy, UV/Vis spectroscopy, flash photolysis, and steady-state irradiation. Of all the network species, the flavylium cation possesses the highest affinity for cucurbit[7]uril. The rate of interconversion between flavylium cation and the basic species (where trans-chalcone is dominant) is approximately nine times lower inside the cucurbit[7]uril. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An efficient graph theory based method to identify every minimal reaction set in a metabolic network

PubMed Central

2014-01-01

Background Development of cells with minimal metabolic functionality is gaining importance due to their efficiency in producing chemicals and fuels. Existing computational methods to identify minimal reaction sets in metabolic networks are computationally expensive. Further, they identify only one of the several possible minimal reaction sets. Results In this paper, we propose an efficient graph theory based recursive optimization approach to identify all minimal reaction sets. Graph theoretical insights offer systematic methods to not only reduce the number of variables in math programming and increase its computational efficiency, but also provide efficient ways to find multiple optimal solutions. The efficacy of the proposed approach is demonstrated using case studies from Escherichia coli and Saccharomyces cerevisiae. In case study 1, the proposed method identified three minimal reaction sets each containing 38 reactions in Escherichia coli central metabolic network with 77 reactions. Analysis of these three minimal reaction sets revealed that one of them is more suitable for developing minimal metabolism cell compared to other two due to practically achievable internal flux distribution. In case study 2, the proposed method identified 256 minimal reaction sets from the Saccharomyces cerevisiae genome scale metabolic network with 620 reactions. The proposed method required only 4.5 hours to identify all the 256 minimal reaction sets and has shown a significant reduction (approximately 80%) in the solution time when compared to the existing methods for finding minimal reaction set. Conclusions Identification of all minimal reactions sets in metabolic networks is essential since different minimal reaction sets have different properties that effect the bioprocess development. The proposed method correctly identified all minimal reaction sets in a both the case studies. The proposed method is computationally efficient compared to other methods for finding minimal reaction sets and useful to employ with genome-scale metabolic networks. PMID:24594118

Minimum-Time and Vibration Avoidance Attitude Maneuver for Spacecraft with Torque and Momentum Limit Constraints in Redundant Reaction Wheel Configuration

NASA Technical Reports Server (NTRS)

Ha, Kong Q.; Femiano, Michael D.; Mosier, Gary E.

2004-01-01

In this paper, we present an optimal open-loop slew trajectory algorithm developed at GSFC for the so-called "Yardstick design" of the James Webb Space Telescope (JWST). JWST is an orbiting infrared observatory featuring a lightweight, segmented primary mirror approximately 6 meters in diameter and a sunshield approximately the size of a tennis court. This large, flexible structure will have significant number of lightly damped, dominant flexible modes. With very stringent requirements on pointing accuracy and image quality, it is important that slewing be done within the required time constraint and with minimal induced vibration in order to maximize observing efficiency. With reaction wheels as control actuators, initial wheel speeds as well as individual wheel torque and momentum limits become dominant constraints in slew performance. These constraints must be taken into account when performing slews to ensure that unexpected reaction wheel saturation does not occur, since such saturation leads to control failure in accurately tracking commanded motion and produces high frequency torque components capable of exciting structural modes. A minimum-time constraint is also included and coupled with reaction wheel limit constraints in the optimization to minimize both the effect of the control torque on the flexible body motion and the maneuver time. The optimization is on slew command parameters, such as maximum slew velocity and acceleration, for a given redundant reaction wheel configuration and is based on the dynamic interaction between the spacecraft and reaction wheel motion. Analytical development of the slew algorithm to generate desired slew position, rate, and acceleration profiles to command a feedback/feed forward control system is described. High-fidelity simulation and experimental results are presented to show that the developed slew law achieves the objectives.

A Memory-Based Model of Hick's Law

ERIC Educational Resources Information Center

Schneider, Darryl W.; Anderson, John R.

2011-01-01

We propose and evaluate a memory-based model of Hick's law, the approximately linear increase in choice reaction time with the logarithm of set size (the number of stimulus-response alternatives). According to the model, Hick's law reflects a combination of associative interference during retrieval from declarative memory and occasional savings…

Chemical Reactions in Turbulent Mixing Flows.

DTIC Science & Technology

1986-04-10

fluctuation of the " flame " length of such reactingjeatreent wer copoit sequencd shout tnhawate facility, documented previously’,’ 1 , using laser jets. A...motion film of such a chemically reacting turbulent jet visualized using this technique, is shown in figure 1. In each I. Flame length fluctuations of...acid-base reaction to determine length and time to allow a simultaneous view of mixing in the two scales for the flame length fluctuations of thin

Detection of Cholera Toxin by Optical Methods: A Mechanism-Based Approach to the Generic Detection of Protein Toxins.

DTIC Science & Technology

1997-04-01

Reaction of NAD and NBAG ......................... 9 2 Time Course of ADP-Ribosylation of LAME and Agmatine with eNAD and Cholera Toxin Fragment A...11 TABLES 1 Retention of eNAD by Dowex 1 . ................................ 13 2 Reaction of LAME and Agmatine with Fluorochromes...14 3 Sensitivity of Detection of LAME and Agmatine by Fluorescamine ......... 15 4 Retention of LAME and Agmatine by Dowex 50

Highly specific enrichment of N-glycoproteome through a nonreductive amination reaction using Fe3O4@SiO2-aniline nanoparticles.

PubMed

Zhang, Ying; Yu, Meng; Zhang, Cheng; Wang, Yali; Di, Yi; Wang, Changchun; Lu, Haojie

2015-04-07

A novel method based on the conjunction of aldehydes from oxidized glycopeptides to aniline groups on magnetic nanoparticles via nonreductive amination is reported for the highly selective enrichment of N-glycopeptides. For the first time, a nonreductive amination reaction has been introduced into N-glycoproteome extraction, and correspondingly a new type of aniline-functionalized nanoparticle has been designed and synthesized.

Coupling of hydrologic transport and chemical reactions in a stream affected by acid mine drainage

USGS Publications Warehouse

Kimball, B.A.; Broshears, R.E.; Bencala, K.E.; McKnight, Diane M.

1994-01-01

Experiments in St. Kevin Gulch, an acid mine drainage stream, examined the coupling of hydrologic transport to chemical reactions affecting metal concentrations. Injection of LiCl as a conservative tracer was used to determine discharge and residence time along a 1497-m reach. Transport of metals downstream from inflows of acidic, metal-rich water was evaluated based on synoptic samples of metal concentrations and the hydrologic characteristics of the stream. Transport of SO4 and Mn was generally conservative, but in the subreaches most affected by acidic inflows, transport was reactive. Both 0.1-??m filtered and particulate Fe were reactive over most of the stream reach. Filtered Al partitioned to the particulate phase in response to high instream concentrations. Simulations that accounted for the removal of SO4, Mn, Fe, and Al with first-order reactions reproduced the steady-state profiles. The calculated rate constants for net removal used in the simulations embody several processes that occur on a stream-reach scale. The comparison between rates of hydrologie transport and chemical reactions indicates that reactions are only important over short distances in the stream near the acidic inflows, where reactions occur on a comparable time scale with hydrologic transport and thus affect metal concentrations.

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

Bandyopadhyay, S.; Chowdhury, R.; Biswas, G.K.

A mathematical model based on the mechanistic approach to the reaction kinetics of pyrolysis reactions and the realistic analysis of the interaction between simultaneous heat and mass transfer along with the chemical reaction has been developed for the design of smoothly running pyrolyzers. The model of a fixed-bed pyrolysis reactor has been proposed on the basis of the dimensionless parameters with respect to time and radial position. The variation of physical parameters like bed voidage, heat capacity, diffusivity, density, thermal conductivity, etc., on temperature and conversion has been taken into account. A deactivation model has also been incorporated to explainmore » the behavior of pyrolysis reactions at temperatures above 673 K. The simulated results of the model have been explained by comparing them with the experimental results.« less

Development of various reaction abilities and their relationships with favorite play activities in preschool children.

PubMed

Miyaguchi, Kazuyoshi; Demura, Shinich; Sugiura, Hiroki; Uchiyama, Masanobu; Noda, Masahiro

2013-10-01

This study examines the development of various reaction movements in preschool children and the relationship between reaction times and favorite play activities. The subjects were 167 healthy preschool children aged 4-6 (96 boys and 71 girls). This study focused on the reaction times of the upper limbs (reaction 1: release; reaction 2: press) and the whole body (reaction 3: forward jump). The activities frequently played in preschools are largely divided into dynamic play activities (tag, soccer, gymnastics set, dodge ball, and jump rope) and static play activities (drawing, playing house, reading, playing with sand, and building blocks). The subjects chose 3 of 10 cards picturing their favorite play activities, depicting 10 different activities. All intraclass correlation coefficients of measured reaction times were high (0.73-0.79). In addition, each reaction time shortened with age. Reaction 1 showed a significant and low correlation with reaction 3 (r = 0.37). The effect size of the whole body reaction time was the largest. Whole body reaction movement, which is largely affected by the exercise output function, develops remarkably in childhood. Children who liked "tag" were faster in all reaction times. The children who chose "soccer" were faster in reactions 2 and 3. In contrast, children who liked "playing house" tended to have slower reaction times. Dynamic activities, such as tag and soccer, promote development of reaction speed and agility in movements involving the whole body. Preschool teachers and physical educators should re-examine the effect of tag and use it periodically as one of the exercise programs to avoid unexpected falls and injuries in everyday life.

Rapid Waterborne Pathogen Detection with Mobile Electronics.

PubMed

Wu, Tsung-Feng; Chen, Yu-Chen; Wang, Wei-Chung; Kucknoor, Ashwini S; Lin, Che-Jen; Lo, Yu-Hwa; Yao, Chun-Wei; Lian, Ian

2017-06-09

Pathogen detection in water samples, without complex and time consuming procedures such as fluorescent-labeling or culture-based incubation, is essential to public safety. We propose an immunoagglutination-based protocol together with the microfluidic device to quantify pathogen levels directly from water samples. Utilizing ubiquitous complementary metal-oxide-semiconductor (CMOS) imagers from mobile electronics, a low-cost and one-step reaction detection protocol is developed to enable field detection for waterborne pathogens. 10 mL of pathogen-containing water samples was processed using the developed protocol including filtration enrichment, immune-reaction detection and imaging processing. The limit of detection of 10 E. coli O157:H7 cells/10 mL has been demonstrated within 10 min of turnaround time. The protocol can readily be integrated into a mobile electronics such as smartphones for rapid and reproducible field detection of waterborne pathogens.

Shock-to-detonation transition of nitromethane: Time-resolved emission spectroscopy measurements

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

Bouyer, Viviane; Darbord, Isabelle; Herve, Philippe

2006-01-01

The objective of this work is to improve the knowledge of the shock-to-detonation transition of nitromethane. The study is based on a spectral analysis in the range 0.3-0.85 {mu}m, with a 28-nm resolution, during experiments of plane shock impacts on explosive targets at 8.6 GPa. The time-resolved radiant spectra show that the detonation front, the reaction products produced during the superdetonation, and the detonation products are semitransparent. The temperature and absorption coefficient profiles are determined from the measured spectra by a mathematical inversion method based on the equation of radiative transfer with Rayleigh scattering regime. Shocked nitromethane reaches at leastmore » 2500 K, showing the existence of local chemical reactions after shock entrance. Levels of temperature of superdetonation and steady-state detonation are also determined.« less

Conventional and microwave assisted synthesis of pyrazolone Mannich bases possessing anti-inflammatory, analgesic, ulcerogenic effect and antimicrobial properties.

PubMed

Sivakumar, Kullampalayam Krishnasamy; Rajasekaran, Aiyalu; Senthilkumar, Palaniappan; Wattamwar, Prasad P

2014-07-01

In the present study, an efficient synthesis of some Mannich base of 5-methyl-2-[(2-oxo-2H-chromen-3-yl)carbonyl]-2,4-dihydro-3H-pyrazol-3-one (4a-j) have been described by using conventional and non-conventional (microwave) techniques. Microwave assisted reactions showed that require shorter reaction time and good yield. The newly synthesized compounds were screened for their anti-inflammatory, analgesic activity, antioxidant, and antibacterial effects were compared with standard drug. Among the compounds studied, compound (4f) showing nearly equipotent anti-inflammatory and analgesic activity than the standard drug (indomethacin), along with minimum ulcerogenic index. Compounds (4b and 4i) showing 1.06 times more active than ciprofloxacin against tested Gram-negative bacteria. Copyright © 2014 Elsevier Ltd. All rights reserved.

Extreme reaction times determine fluctuation scaling in human color vision

NASA Astrophysics Data System (ADS)

Medina, José M.; Díaz, José A.

2016-11-01

In modern mental chronometry, human reaction time defines the time elapsed from stimulus presentation until a response occurs and represents a reference paradigm for investigating stochastic latency mechanisms in color vision. Here we examine the statistical properties of extreme reaction times and whether they support fluctuation scaling in the skewness-kurtosis plane. Reaction times were measured for visual stimuli across the cardinal directions of the color space. For all subjects, the results show that very large reaction times deviate from the right tail of reaction time distributions suggesting the existence of dragon-kings events. The results also indicate that extreme reaction times are correlated and shape fluctuation scaling over a wide range of stimulus conditions. The scaling exponent was higher for achromatic than isoluminant stimuli, suggesting distinct generative mechanisms. Our findings open a new perspective for studying failure modes in sensory-motor communications and in complex networks.

Using reflection time-of-flight mass spectrometer techniques to investigate cluster dynamics and bonding

NASA Astrophysics Data System (ADS)

Wei, Shiqing; Castleman, A. W., Jr.

1994-02-01

Lase based time-of-flight mass spectrometer systems affixed with reflectrons are valuable tools for investigating cluster dynamics and reactions, spectroscopy and structures. Utilizing the reflectron time-of-flight mass spectrometer techniques, both decay fractions and kinetic energy releases of metastable cluster ions can be measured with high precision. By applying related theoretical models, the desired thermochemical values of metastable species can be deduced, which are otherwise very difficult to obtain. Several examples are discussed with attention focused on ammonia as a test case for hydrogen bond systems, and xenon for weaker van der Waals clusters. A brief overview of applications to investigating solvation effects on reactions and structures, delayed electron transfer and ionization through intracluster Penning ionization is also given.

Diffraction-based optical correlator

NASA Technical Reports Server (NTRS)

Spremo, Stevan M. (Inventor); Fuhr, Peter L. (Inventor); Schipper, John F. (Inventor)

2005-01-01

Method and system for wavelength-based processing of a light beam. A light beam, produced at a chemical or physical reaction site and having at least first and second wavelengths, ?1 and ?2, is received and diffracted at a first diffraction grating to provide first and second diffracted beams, which are received and analyzed in terms of wavelength and/or time at two spaced apart light detectors. In a second embodiment, light from first and second sources is diffracted and compared in terms of wavelength and/or time to determine if the two beams arise from the same source. In a third embodiment, a light beam is split and diffracted and passed through first and second environments to study differential effects. In a fourth embodiment, diffracted light beam components, having first and second wavelengths, are received sequentially at a reaction site to determine whether a specified reaction is promoted, based on order of receipt of the beams. In a fifth embodiment, a cylindrically shaped diffraction grating (uniform or chirped) is rotated and translated to provide a sequence of diffracted beams with different wavelengths. In a sixth embodiment, incident light, representing one or more symbols, is successively diffracted from first and second diffraction gratings and is received at different light detectors, depending upon the wavelengths present in the incident light.

PCR deduction of invasive and colonizing pneumococcal serotypes from Venezuela: a critical appraisal.

PubMed

Bello Gonzalez, Teresita; Rivera-Olivero, Ismar Alejandra; Sisco, María Carolina; Spadola, Enza; Hermans, Peter W; de Waard, Jacobus H

2014-04-15

Serotype surveillance of Streptococcus pneumoniae is indispensable for evaluating the potential impact of pneumococcal conjugate vaccines. Serotyping by the standard Quellung reaction is technically demanding, time consuming, and expensive. A simple and economical strategy is multiplex PCR-based serotyping. We evaluated the cost effectiveness of a modified serial multiplex PCR (mPCR), resolving 24 serotypes in four PCR reactions and optimally targeting the most prevalent invasive and colonizing pneumococcal serotypes found in Venezuela. A total of 223 pneumococcal isolates, 140 invasive and 83 carriage isolates, previously serotyped by the Quellung reaction and representing the 18 most common serotypes/groups identified in Venezuela, were serotyped with the adapted mPCR. The mPCR serotyped 76% of all the strains in the first two PCR reactions and 91% after four reactions, correctly identifying 17 serotypes/groups. An isolate could be serotyped with mPCR in less than 2 minutes versus 15 minutes for the Quellung reaction, considerably lowering labor costs. A restrictive weakness of mPCR was found for the detection of 19F strains. Most Venezuelan 19F strains were not typeable using the mPCR, and two 19F cps serotype variants were identified. The mPCR assay is an accurate, rapid, and economical method for the identification of the vast majority of the serotypes from Venezuela and can be used in place of the standard Quellung reaction. An exception is the identification of serotype 19F. In this setting, most 19F strains were not detectable with mPCR, demonstrating a need of serology-based quality control for PCR-based serotyping.

A novel, multiplex, real-time PCR-based approach for the detection of the commonly occurring pathogenic fungi and bacteria.

PubMed

Horváth, Ádám; Pető, Zoltán; Urbán, Edit; Vágvölgyi, Csaba; Somogyvári, Ferenc

2013-12-23

Polymerase chain reaction (PCR)-based techniques are widely used to identify fungal and bacterial infections. There have been numerous reports of different, new, real-time PCR-based pathogen identification methods although the clinical practicability of such techniques is not yet fully clarified.The present study focuses on a novel, multiplex, real-time PCR-based pathogen identification system developed for rapid differentiation of the commonly occurring bacterial and fungal causative pathogens of bloodstream infections. A multiplex, real-time PCR approach is introduced for the detection and differentiation of fungi, Gram-positive (G+) and Gram-negative (G-) bacteria. The Gram classification is performed with the specific fluorescence resonance energy transfer (FRET) probes recommended for LightCycler capillary real-time PCR. The novelty of our system is the use of a non-specific SYBR Green dye instead of labelled anchor probes or primers, to excite the acceptor dyes on the FRET probes. In conjunction with this, the use of an intercalating dye allows the detection of fungal amplicons.With the novel pathogen detection system, fungi, G + and G- bacteria in the same reaction tube can be differentiated within an hour after the DNA preparation via the melting temperatures of the amplicons and probes in the same tube. This modified FRET technique is specific and more rapid than the gold-standard culture-based methods. The fact that fungi, G + and G- bacteria were successfully identified in the same tube within an hour after the DNA preparation permits rapid and early evidence-based management of bloodstream infections in clinical practice.

Effects of reaction time variability and age on brain activity during Stroop task performance.

PubMed

Tam, Angela; Luedke, Angela C; Walsh, Jeremy J; Fernandez-Ruiz, Juan; Garcia, Angeles

2015-09-01

Variability in reaction time during task performance may reflect fluctuations in attention and cause reduced performance in goal-directed tasks, yet it is unclear whether the mechanisms behind this phenomenon change with age. Using fMRI, we tested young and cognitively healthy older adults with the Stroop task to determine whether aging affects the neural mechanisms underlying intra-individual reaction time variability. We found significant between-group differences in BOLD activity modulated by reaction time. In older adults, longer reaction times were associated with greater activity in frontoparietal attentional areas, while in younger adults longer reaction times were associated with greater activity in default mode network areas. Our results suggest that the neural correlates of reaction time variability change with healthy aging, reinforcing the concept of functional plasticity to maintain high cognitive function throughout the lifespan.

Assays for the determination of the activity of DNA nucleases based on the fluorometric properties of the YOYO dye.

PubMed

Fernández-Sierra, Mónica; Quiñones, Edwin

2015-03-15

Here we characterize the fluorescence of the YOYO dye as a tool for studying DNA-protein interactions in real time and present two continuous YOYO-based assays for sensitively monitoring the kinetics of DNA digestion by λ-exonuclease and the endonuclease EcoRV. The described assays rely on the different fluorescence intensities between single- and double-stranded DNA-YOYO complexes, allowing straightforward determination of nuclease activity and quantitative determination of reaction products. The assays were also employed to assess the effect of single-stranded DNA-binding proteins on the λ-exonuclease reaction kinetics, showing that the extreme thermostable single-stranded DNA-binding protein (ET-SSB) significantly reduced the reaction rate, while the recombination protein A (RecA) displayed no effect. Copyright © 2015 Elsevier Inc. All rights reserved.

One-step gas-solid reaction synthesis of W@WS2 nanorattles and their novel catalytic activity.

PubMed

Wen, Yan; Zhang, Haijun; Zhang, Shaowei

2014-11-07

W@WS2 nanorattles were synthesised by heating a mixture of WO3 nanoparticles and S at a relatively low temperature between 750 and 950 °C in H2/Ar. In addition to the temperature, the competition between the H2 reduction and the S sulphidation sub-reactions dominated the reaction mechanisms and the morphologies of final products. Based on this, several types of nanostructures, including WS2 nanoflakes, inorganic fullerene-like nanoparticles and W@WS2 nanorattles (with desirable core size and shell thickness), could be selectively prepared by simply tailoring the processing parameters. Moreover, it was found for the first time that as-prepared W@WS2 nanorattles exhibited excellent catalytic activities which were close to or even better than their much more costive Au-based counterparts.

One-step gas-solid reaction synthesis of W@WS2 nanorattles and their novel catalytic activity

NASA Astrophysics Data System (ADS)

Wen, Yan; Zhang, Haijun; Zhang, Shaowei

2014-10-01

W@WS2 nanorattles were synthesised by heating a mixture of WO3 nanoparticles and S at a relatively low temperature between 750 and 950 °C in H2/Ar. In addition to the temperature, the competition between the H2 reduction and the S sulphidation sub-reactions dominated the reaction mechanisms and the morphologies of final products. Based on this, several types of nanostructures, including WS2 nanoflakes, inorganic fullerene-like nanoparticles and W@WS2 nanorattles (with desirable core size and shell thickness), could be selectively prepared by simply tailoring the processing parameters. Moreover, it was found for the first time that as-prepared W@WS2 nanorattles exhibited excellent catalytic activities which were close to or even better than their much more costive Au-based counterparts.

Neutron measurements from beam-target reactions at the ELISE neutral beam test facility

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

Xufei, X., E-mail: xiexufei@pku.edu.cn; Fan, T.; Nocente, M.

2014-11-15

Measurements of 2.5 MeV neutron emission from beam-target reactions performed at the ELISE neutral beam test facility are presented in this paper. The measurements are used to study the penetration of a deuterium beam in a copper dump, based on the observation of the time evolution of the neutron counting rate from beam-target reactions with a liquid scintillation detector. A calculation based on a local mixing model of deuterium deposition in the target up to a concentration of 20% at saturation is used to evaluate the expected neutron yield for comparison with data. The results are of relevance to understandmore » neutron emission associated to beam penetration in a solid target, with applications to diagnostic systems for the SPIDER and MITICA Neutral Beam Injection prototypes.« less

Spontaneous Fluctuations in Sensory Processing Predict Within-Subject Reaction Time Variability.

PubMed

Ribeiro, Maria J; Paiva, Joana S; Castelo-Branco, Miguel

2016-01-01

When engaged in a repetitive task our performance fluctuates from trial-to-trial. In particular, inter-trial reaction time variability has been the subject of considerable research. It has been claimed to be a strong biomarker of attention deficits, increases with frontal dysfunction, and predicts age-related cognitive decline. Thus, rather than being just a consequence of noise in the system, it appears to be under the control of a mechanism that breaks down under certain pathological conditions. Although the underlying mechanism is still an open question, consensual hypotheses are emerging regarding the neural correlates of reaction time inter-trial intra-individual variability. Sensory processing, in particular, has been shown to covary with reaction time, yet the spatio-temporal profile of the moment-to-moment variability in sensory processing is still poorly characterized. The goal of this study was to characterize the intra-individual variability in the time course of single-trial visual evoked potentials and its relationship with inter-trial reaction time variability. For this, we chose to take advantage of the high temporal resolution of the electroencephalogram (EEG) acquired while participants were engaged in a 2-choice reaction time task. We studied the link between single trial event-related potentials (ERPs) and reaction time using two different analyses: (1) time point by time point correlation analyses thereby identifying time windows of interest; and (2) correlation analyses between single trial measures of peak latency and amplitude and reaction time. To improve extraction of single trial ERP measures related with activation of the visual cortex, we used an independent component analysis (ICA) procedure. Our ERP analysis revealed a relationship between the N1 visual evoked potential and reaction time. The earliest time point presenting a significant correlation of its respective amplitude with reaction time occurred 175 ms after stimulus onset, just after the onset of the N1 peak. Interestingly, single trial N1 latency correlated significantly with reaction time, while N1 amplitude did not. In conclusion, our findings suggest that inter-trial variability in the timing of extrastriate visual processing contributes to reaction time variability.

Spontaneous Fluctuations in Sensory Processing Predict Within-Subject Reaction Time Variability

PubMed Central

Ribeiro, Maria J.; Paiva, Joana S.; Castelo-Branco, Miguel

2016-01-01

When engaged in a repetitive task our performance fluctuates from trial-to-trial. In particular, inter-trial reaction time variability has been the subject of considerable research. It has been claimed to be a strong biomarker of attention deficits, increases with frontal dysfunction, and predicts age-related cognitive decline. Thus, rather than being just a consequence of noise in the system, it appears to be under the control of a mechanism that breaks down under certain pathological conditions. Although the underlying mechanism is still an open question, consensual hypotheses are emerging regarding the neural correlates of reaction time inter-trial intra-individual variability. Sensory processing, in particular, has been shown to covary with reaction time, yet the spatio-temporal profile of the moment-to-moment variability in sensory processing is still poorly characterized. The goal of this study was to characterize the intra-individual variability in the time course of single-trial visual evoked potentials and its relationship with inter-trial reaction time variability. For this, we chose to take advantage of the high temporal resolution of the electroencephalogram (EEG) acquired while participants were engaged in a 2-choice reaction time task. We studied the link between single trial event-related potentials (ERPs) and reaction time using two different analyses: (1) time point by time point correlation analyses thereby identifying time windows of interest; and (2) correlation analyses between single trial measures of peak latency and amplitude and reaction time. To improve extraction of single trial ERP measures related with activation of the visual cortex, we used an independent component analysis (ICA) procedure. Our ERP analysis revealed a relationship between the N1 visual evoked potential and reaction time. The earliest time point presenting a significant correlation of its respective amplitude with reaction time occurred 175 ms after stimulus onset, just after the onset of the N1 peak. Interestingly, single trial N1 latency correlated significantly with reaction time, while N1 amplitude did not. In conclusion, our findings suggest that inter-trial variability in the timing of extrastriate visual processing contributes to reaction time variability. PMID:27242470

When does a good working memory counteract proactive interference? Surprising evidence from a probe recognition task.

PubMed

Cowan, Nelson; Saults, J Scott

2013-02-01

It is often proposed that individuals with high working memory span overcome proactive interference (PI) from previous trials, saving working memory for task-relevant items. We examined this hypothesis in word-list probe recognition. We found no difference in PI related to span. Instead, ex-gaussian analysis of reaction time showed speed advantages for high spans specific to short lists (3 or 4 items) but absent from longer lists (6 or 8 items). We suggest that high-span advantages in reaction time are based on finesse during easy trials, not on overcoming PI. 2013 APA, all rights reserved

Tuberculin immunotherapy: its history and lessons to be learned.

PubMed

Vilaplana, Cristina; Cardona, Pere-Joan

2010-02-01

The use of tuberculin for the therapy of tuberculosis was attempted more than 100 years ago and abandoned because of its adverse reactions. In this historical review we point out that some of the intensive efforts to avoid the reactions were based on the best scientific rationale available at that time. Balancing the dosage and intervals of tuberculin delivery with clinical and laboratory monitoring of patients achieved a limited success, with implications, toward current research in the field. The role of economical and social aspects at that time is also a lesson to be learned toward current approaches to tuberculosis control. Copyright 2009 Elsevier Masson SAS. All rights reserved.

Shock tube and chemical kinetic modeling study of the oxidation of 2,5-dimethylfuran.

PubMed

Sirjean, Baptiste; Fournet, René; Glaude, Pierre-Alexandre; Battin-Leclerc, Frédérique; Wang, Weijing; Oehlschlaeger, Matthew A

2013-02-21

A detailed kinetic model describing the oxidation of 2,5-dimethylfuran (DMF), a potential second-generation biofuel, is proposed. The kinetic model is based upon quantum chemical calculations for the initial DMF consumption reactions and important reactions of intermediates. The model is validated by comparison to new DMF shock tube ignition delay time measurements (over the temperature range 1300-1831 K and at nominal pressures of 1 and 4 bar) and the DMF pyrolysis speciation measurements of Lifshitz et al. [ J. Phys. Chem. A 1998 , 102 ( 52 ), 10655 - 10670 ]. Globally, modeling predictions are in good agreement with the considered experimental targets. In particular, ignition delay times are predicted well by the new model, with model-experiment deviations of at most a factor of 2, and DMF pyrolysis conversion is predicted well, to within experimental scatter of the Lifshitz et al. data. Additionally, comparisons of measured and model predicted pyrolysis speciation provides validation of theoretically calculated channels for the oxidation of DMF. Sensitivity and reaction flux analyses highlight important reactions as well as the primary reaction pathways responsible for the decomposition of DMF and formation and destruction of key intermediate and product species.

Ethanesulfonic acid-based esterification of industrial acidic crude palm oil for biodiesel production.

PubMed

Hayyan, Adeeb; Mjalli, Farouq S; Hashim, Mohd Ali; Hayyan, Maan; AlNashef, Inas M; Al-Zahrani, Saeed M; Al-Saadi, Mohammed A

2011-10-01

An industrial grade acidic crude palm oil (ACPO) pre-treatment process was carried out using ethanesulfonic acid (ESA) as a catalyst in the esterification reaction. ESA was used in different dosages to reduce free fatty acid (FFA) to a minimum level for the second stage of biodiesel production via alkaline transesterification reaction. Different process operating conditions were optimized such as ESA dosage (0.25-3.5% wt/wt), methanol to ACPO molar ratio (1:1-20:1), reaction temperature (40-70 °C), and reaction time (3-150 min). This study revealed the potential use of abundant quantities of ACPO from oil palm mills for biodiesel production. The lab scale results showed the effectiveness of the pre-treatment process using ESA catalyst. Three consecutive catalyst recycling runs were achieved without significant degradation in its performance. Second and third reuse runs needed more reaction time to achieve the target level of FFA content. Esterification and transesterification using ESA and KOH respectively is proposed for biodiesel industrial scale production. The produced biodiesel meets the international standards specifications for biodiesel fuel (EN 14214 and ASTM D6751). Copyright © 2011 Elsevier Ltd. All rights reserved.

Mixing-controlled reactive transport on travel times in heterogeneous media

NASA Astrophysics Data System (ADS)

Luo, J.; Cirpka, O.

2008-05-01

Modeling mixing-controlled reactive transport using traditional spatial discretization of the domain requires identifying the spatial distributions of hydraulic and reactive parameters including mixing-related quantities such as dispersivities and kinetic mass-transfer coefficients. In most applications, breakthrough curves of conservative and reactive compounds are measured at only a few locations and models are calibrated by matching these breakthrough curves, which is an ill posed inverse problem. By contrast, travel-time based transport models avoid costly aquifer characterization. By considering breakthrough curves measured on different scales, one can distinguish between mixing, which is a prerequisite for reactions, and spreading, which per se does not foster reactions. In the travel-time based framework, the breakthrough curve of a solute crossing an observation plane, or ending in a well, is interpreted as the weighted average of concentrations in an ensemble of non-interacting streamtubes, each of which is characterized by a distinct travel-time value. Mixing is described by longitudinal dispersion and/or kinetic mass transfer along individual streamtubes, whereas spreading is characterized by the distribution of travel times which also determines the weights associated to each stream tube. Key issues in using the travel-time based framework include the description of mixing mechanisms and the estimation of the travel-time distribution. In this work, we account for both apparent longitudinal dispersion and kinetic mass transfer as mixing mechanisms, thus generalizing the stochastic-convective model with or without inter-phase mass transfer and the advective-dispersive streamtube model. We present a nonparametric approach of determining the travel-time distribution, given a breakthrough curve integrated over an observation plane and estimated mixing parameters. The latter approach is superior to fitting parametric models in cases where the true travel-time distribution exhibits multiple peaks or long tails. It is demonstrated that there is freedom for the combinations of mixing parameters and travel-time distributions to fit conservative breakthrough curves and describe the tailing. Reactive transport cases with a bimolecular instantaneous irreversible reaction and a dual Michaelis-Menten problem demonstrate that the mixing introduced by local dispersion and mass transfer may be described by apparent mean mass transfer with coefficients evaluated by local breakthrough curves.

Arrhenius Rate: constant volume burn

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

Menikoff, Ralph

A constant volume burn occurs for an idealized initial state in which a large volume of reactants at rest is suddenly raised to a high temperature and begins to burn. Due to the uniform spatial state, there is no fluid motion and no heat conduction. This reduces the time evolu tion to an ODE for the reaction progress variable. With an Arrhenius reaction rate, two characteristics of thermal ignition are illustrated: induction time and thermal runaway. The Frank-Kamenetskii approximation then leads to a simple expression for the adiabatic induction time. For a first order reaction, the analytic solution is derivedmore » and used to illustrate the effect of varying the activation temperature; in particular, on the induction time. In general, the ODE can be solved numerically. This is used to illustrate the effect of varying the reaction order. We note that for a first order reaction, the time evolution of the reaction progress variable has an exponential tail. In contrast, for a reaction order less than one, the reaction completes in a nite time. The reaction order also affects the induction time.« less

A comparative study of simple auditory reaction time in blind (congenitally) and sighted subjects.

PubMed

Gandhi, Pritesh Hariprasad; Gokhale, Pradnya A; Mehta, H B; Shah, C J

2013-07-01

Reaction time is the time interval between the application of a stimulus and the appearance of appropriate voluntary response by a subject. It involves stimulus processing, decision making, and response programming. Reaction time study has been popular due to their implication in sports physiology. Reaction time has been widely studied as its practical implications may be of great consequence e.g., a slower than normal reaction time while driving can have grave results. To study simple auditory reaction time in congenitally blind subjects and in age sex matched sighted subjects. To compare the simple auditory reaction time between congenitally blind subjects and healthy control subjects. STUDY HAD BEEN CARRIED OUT IN TWO GROUPS: The 1(st) of 50 congenitally blind subjects and 2(nd) group comprises of 50 healthy controls. It was carried out on Multiple Choice Reaction Time Apparatus, Inco Ambala Ltd. (Accuracy±0.001 s) in a sitting position at Government Medical College and Hospital, Bhavnagar and at a Blind School, PNR campus, Bhavnagar, Gujarat, India. Simple auditory reaction time response with four different type of sound (horn, bell, ring, and whistle) was recorded in both groups. According to our study, there is no significant different in reaction time between congenital blind and normal healthy persons. Blind individuals commonly utilize tactual and auditory cues for information and orientation and they reliance on touch and audition, together with more practice in using these modalities to guide behavior, is often reflected in better performance of blind relative to sighted participants in tactile or auditory discrimination tasks, but there is not any difference in reaction time between congenitally blind and sighted people.

End-Member Formulation of Solid Solutions and Reactive Transport

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

Lichtner, Peter C.

2015-09-01

A model for incorporating solid solutions into reactive transport equations is presented based on an end-member representation. Reactive transport equations are solved directly for the composition and bulk concentration of the solid solution. Reactions of a solid solution with an aqueous solution are formulated in terms of an overall stoichiometric reaction corresponding to a time-varying composition and exchange reactions, equivalent to reaction end-members. Reaction rates are treated kinetically using a transition state rate law for the overall reaction and a pseudo-kinetic rate law for exchange reactions. The composition of the solid solution at the onset of precipitation is assumed tomore » correspond to the least soluble composition, equivalent to the composition at equilibrium. The stoichiometric saturation determines if the solid solution is super-saturated with respect to the aqueous solution. The method is implemented for a simple prototype batch reactor using Mathematica for a binary solid solution. Finally, the sensitivity of the results on the kinetic rate constant for a binary solid solution is investigated for reaction of an initially stoichiometric solid phase with an undersaturated aqueous solution.« less

Strategic Control over Extent and Timing of Distractor-Based Response Activation

ERIC Educational Resources Information Center

Jost, Kerstin; Wendt, Mike; Luna-Rodriguez, Aquiles; Löw, Andreas; Jacobsen, Thomas

2017-01-01

In choice reaction time (RT) tasks, performance is often influenced by the presence of nominally irrelevant stimuli, referred to as distractors. Recent research provided evidence that distractor processing can be adjusted to the utility of the distractors: Distractors predictive of the upcoming target/response were more attended to and also…

Spatial optimization of prairie dog colonies for black-footed ferret recovery

Treesearch

Michael Bevers; John G. Hof; Daniel W. Uresk; Gregory L. Schenbeck

1997-01-01

A discrete-time reaction-diffusion model for black-footed ferret release, population growth, and dispersal is combined with ferret carrying capacity constraints based on prairie dog population management decisions to form a spatial optimization model. Spatial arrangement of active prairie dog colonies within a ferret reintroduction area is optimized over time for...

Indirect Measurement of Sexual Orientation: Comparison of the Implicit Relational Assessment Procedure, Viewing Time, and Choice Reaction Time Tasks.

PubMed

Rönspies, Jelena; Schmidt, Alexander F; Melnikova, Anna; Krumova, Rosina; Zolfagari, Asadeh; Banse, Rainer

2015-07-01

The present study was conducted to validate an adaptation of the Implicit Relational Assessment Procedure (IRAP) as an indirect latency-based measure of sexual orientation. Furthermore, reliability and criterion validity of the IRAP were compared to two established indirect measures of sexual orientation: a Choice Reaction Time task (CRT) and a Viewing Time (VT) task. A sample of 87 heterosexual and 35 gay men completed all three indirect measures in an online study. The IRAP and the VT predicted sexual orientation nearly perfectly. Both measures also showed a considerable amount of convergent validity. Reliabilities (internal consistencies) reached satisfactory levels. In contrast, the CRT did not tap into sexual orientation in the present study. In sum, the VT measure performed best, with the IRAP showing only slightly lower reliability and criterion validity, whereas the CRT did not yield any evidence of reliability or criterion validity in the present research. The results were discussed in the light of specific task properties of the indirect latency-based measures (task-relevance vs. task-irrelevance).

The effect of Co-doping on the humidity sensing properties of ordered mesoporous TiO2

NASA Astrophysics Data System (ADS)

Li, Zhong; Haidry, Azhar Ali; Gao, Bin; Wang, Tao; Yao, ZhengJun

2017-08-01

Monitoring of humidity is of utmost importance as it is essential part of almost every process in our life. Many commercial humidity sensors based on metal oxide semiconductors are available in the market, but there is still need to synthesize low-cost, fast and highly sensitive humidity sensors with no interference from background environment. The aim of this work was to fabricate the ordered mesoporous un-doped and Co-doped TiO2 (0.1-5 mol% Co) and to analyze its humidity sensing properties at room temperatures. The ordered mesoporous powders with high specific surface area (SSA) were prepared by multicomponent self-assembly procedure and then spray-coated onto the sensor substrates with interdigitated gold electrodes. The sensors exhibited excellent stability and reproducible resistance change under various relative humidity percentages (9-90% RH) with negligible effect of background environment. For instance, the response to 90% RH at room temperature was about five orders of magnitude (∼1.39 × 105) and the response time (Tres) was ∼24 s. The reaction/recovery times of the sensors were compared with commercial humidity sensor to show that the reaction times in this work are not given by the surface reaction of water vapor on the sensor surfaces, rather these are mainly influenced by the experimental setup. The sensor response increased up to 3 mol% Co-contents and then decreased for 5 mol% Co-contents. Based on the experimental results, the surface reaction of humidity is discussed related to specific surface area, average grain size and cobalt contents to understand the humidity sensing mechanism.

Inter-session reliability and sex-related differences in hamstrings total reaction time, pre-motor time and motor time during eccentric isokinetic contractions in recreational athlete.

PubMed

Ayala, Francisco; De Ste Croix, Mark; Sainz de Baranda, Pilar; Santonja, Fernando

2014-04-01

The purposes were twofold: (a) to ascertain the inter-session reliability of hamstrings total reaction time, pre-motor time and motor time; and (b) to examine sex-related differences in the hamstrings reaction times profile. Twenty-four men and 24 women completed the study. Biceps femoris and semitendinosus total reaction time, pre-motor time and motor time measured during eccentric isokinetic contractions were recorded on three different occasions. Inter-session reliability was examined through typical percentage error (CVTE), percentage change in the mean (CM) and intraclass correlations (ICC). For both biceps femoris and semitendinosus, total reaction time, pre-motor time and motor time measures demonstrated moderate inter-session reliability (CVTE<10%; CM<3%; ICC>0.7). The results also indicated that, although not statistically significant, women reported consistently longer hamstrings total reaction time (23.5ms), pre-motor time (12.7ms) and motor time (7.5ms) values than men. Therefore, an observed change larger than 5%, 9% and 8% for total reaction time, pre-motor time and motor time respectively from baseline scores after performing a training program would indicate that a real change was likely. Furthermore, while not statistically significant, sex differences were noted in the hamstrings reaction time profile which may play a role in the greater incidence of ACL injuries in women. Copyright © 2013 Elsevier Ltd. All rights reserved.

Reaction cycle and thermodynamics in bacteriorhodopsin

NASA Technical Reports Server (NTRS)

Lanyi, J. K.

1992-01-01

Light causes the all-trans to 13-cis isomerization of the retinal in bacteriorhodopsin; the thermal relaxation leading back to the initial state drives proton transport first via proton transfer between the retinal Schiff base and D85 and then between the Schiff base and D96. The reaction sequence and thermodynamics of this photocycle are described by measuring time-resolved absorption changes with a gated multichannel analyzer between 100 ns and 100 ms, at six temperatures between 5 degrees C and 30 degrees C. Analysis of the energetics of the chromophore reaction sequence is on the basis of a recently proposed model (Varo & Lanyi, Biochemistry 30, 5016-5022, 1991) which consists of a single cycle and many reversible reactions: BR -hv-->K<==>L<==>M1-->M2<==>N<==>O-->BR. The existence of the M1-->M2 reaction, which functions as the switch in the proton transfer, is confirmed by spectroscopic evidence. The calculated thermodynamic parameters indicate that the exchange of free energy between the protein and the protons is at the switch step. Further, a large entropy decrease at this reaction suggests a protein conformation change which will conserve delta G for driving the completion of the reaction cycle. The results provide insights to mechanism and energy coupling in this system, with possible relevance to the general question of how ion pumps function.

Photooxidation of 3-substituted pyrroles:  a postcolumn reaction detection system for singlet molecular oxygen in HPLC.

PubMed

Denham, K; Milofsky, R E

1998-10-01

A postcolumn photochemical reaction detection scheme, based on the reaction of 3-substituted pyrroles with singlet molecular oxygen ((1)O(2)), has been developed. The method is selective and sensitive for the determination of a class of organic compounds called (1)O(2)-sensitizers and is readily coupled to HPLC. Following separation by HPLC, analytes ((1)O(2)-sensitizers) are excited by a Hg pen-ray lamp. Analytes that are efficient (1)O(2)-sensitizers promote ground-state O(2) ((3)Σ(g)(-)) to an excited state ((1)Σ(g)(+) or (1)Δ(g)), which reacts rapidly with tert-butyl-3,4,5-trimethylpyrrolecarboxylate (BTMPC) or N-benzyl-3-methoxypyrrole-2-tert-carboxylate (BMPC), which is added to the mobile phase. Detection is based on the loss of pyrrole (BTMPC or BMPC). The reaction is catalytic in nature since one analyte molecule may absorb light many times, producing large amounts of (1)O(2). Detection limits for several (1)O(2)-sensitizers were improved by 1-2 orders of magnitude over optimized UV-absorbance detection. This paper discusses the optimization of the reaction conditions for this photochemical reaction detection scheme and its application to the detection of PCBs, nitrogen heterocycles, nitro and chloro aromatics, and other substituted aromatic compounds.

Behavioral and Neural Sustained Attention Deficits in Bipolar Disorder and Familial Risk of Bipolar Disorder.

PubMed

Pagliaccio, David; Wiggins, Jillian Lee; Adleman, Nancy E; Harkins, Elizabeth; Curhan, Alexa; Towbin, Kenneth E; Brotman, Melissa A; Pine, Daniel S; Leibenluft, Ellen

2017-11-01

Few neuroimaging studies compare individuals affected with bipolar disorder (BP), at high familial risk of BP, and at low risk to identify endophenotypes for BP. None have examined variability in attention, despite promising behavioral work in this area. We used functional magnetic resonance imaging (fMRI) methods uniquely powered to compare the neural correlates of attention variability in these three groups. The present study examined 8- to 25-year-old individuals (n = 106) who completed an fMRI attention task: 24 with BP, 29 at risk based on a first-degree relative with BP, and 53 healthy, low-risk individuals. Group differences in intrasubject variability in reaction time were examined, and a sophisticated fMRI analytic approach was used to quantify precisely trialwise associations between reaction time and brain activity. The latter has not been examined previously in BP or risk of BP. Relative to healthy individuals, those with BP or at risk for BP exhibited increased reaction time variability (F 2,102 = 4.26, p = .02, η p 2 = .08). Importantly, we identified blunted relationships between trialwise variation in reaction time and brain activity in the inferior and middle frontal gyri, precuneus, cingulate cortex, caudate, and postcentral gyrus (all regions: p < .001, η p 2 > .06) in both at-risk and BP individuals compared with healthy, low-risk individuals. This blunting partially mediated group differences in reaction time variability (β = .010, 95% confidence interval 0.002 to 0.020, Sobel Z = 2.08, p = .038). Blunting in key frontal, cingulate, and striatal areas was evident in unaffected, at-risk individuals and in euthymic BP patients. Elucidating such novel neural endophenotypes can facilitate new approaches to BP prediction, diagnosis, and prevention. Published by Elsevier Inc.

Optimal multisensory decision-making in a reaction-time task.

PubMed

Drugowitsch, Jan; DeAngelis, Gregory C; Klier, Eliana M; Angelaki, Dora E; Pouget, Alexandre

2014-06-14

Humans and animals can integrate sensory evidence from various sources to make decisions in a statistically near-optimal manner, provided that the stimulus presentation time is fixed across trials. Little is known about whether optimality is preserved when subjects can choose when to make a decision (reaction-time task), nor when sensory inputs have time-varying reliability. Using a reaction-time version of a visual/vestibular heading discrimination task, we show that behavior is clearly sub-optimal when quantified with traditional optimality metrics that ignore reaction times. We created a computational model that accumulates evidence optimally across both cues and time, and trades off accuracy with decision speed. This model quantitatively explains subjects's choices and reaction times, supporting the hypothesis that subjects do, in fact, accumulate evidence optimally over time and across sensory modalities, even when the reaction time is under the subject's control.

Transesterification of palm oil using sodium silicate base catalyst from geothermal sludge

NASA Astrophysics Data System (ADS)

Perdana, I.; Nugrahanti, N.; Sofiyah; Bendiyasa, I. M.

2016-11-01

The use of solid base catalysts in biodiesel synthesis is becoming more preferable because of their superiority over homogeneous catalysts. In the present work, a strong base catalyst of sodium silicate synthesized from silica-rich geothermal sludge was used in a transesterification of palm oil with methanol. The catalyst was calcined at 400°C for three hours with a temperature ramp of 20°C/min. The transesterification was carried out at varying temperature in the range of 50 - 70°C for 60 minutes with a methanol-palm oil molar ratio of 8.8:1. The catalyst-palm oil ratio was varied in the range of 1 - 5% (w/w). In order to investigate kinetics of reaction, at a certain interval of time samples were taken consecutively during the reaction. Experimental results showed that the sodium silicate was very active in the transesterification of palm oil with methanol. Reaction temperature at 60°C was sufficient to reach a conversion level as high as 93% in a relatively short reaction period. Meanwhile, the high conversion was still achievable with the use of 1 % (w/w) catalyst. In addition, a lumped model of reaction kinetics was adequate to approach the experimental data with a calculated activation energy of 15.73 kcal/mole. Results of the present work suggested that sodium silicate synthesized from local resources of geothermal sludge would become potential solid base catalyst in biodiesel synthesis.

Sparse Regression Based Structure Learning of Stochastic Reaction Networks from Single Cell Snapshot Time Series.

PubMed

Klimovskaia, Anna; Ganscha, Stefan; Claassen, Manfred

2016-12-01

Stochastic chemical reaction networks constitute a model class to quantitatively describe dynamics and cell-to-cell variability in biological systems. The topology of these networks typically is only partially characterized due to experimental limitations. Current approaches for refining network topology are based on the explicit enumeration of alternative topologies and are therefore restricted to small problem instances with almost complete knowledge. We propose the reactionet lasso, a computational procedure that derives a stepwise sparse regression approach on the basis of the Chemical Master Equation, enabling large-scale structure learning for reaction networks by implicitly accounting for billions of topology variants. We have assessed the structure learning capabilities of the reactionet lasso on synthetic data for the complete TRAIL induced apoptosis signaling cascade comprising 70 reactions. We find that the reactionet lasso is able to efficiently recover the structure of these reaction systems, ab initio, with high sensitivity and specificity. With only < 1% false discoveries, the reactionet lasso is able to recover 45% of all true reactions ab initio among > 6000 possible reactions and over 102000 network topologies. In conjunction with information rich single cell technologies such as single cell RNA sequencing or mass cytometry, the reactionet lasso will enable large-scale structure learning, particularly in areas with partial network structure knowledge, such as cancer biology, and thereby enable the detection of pathological alterations of reaction networks. We provide software to allow for wide applicability of the reactionet lasso.

Development of a screening method for genetically modified soybean by plasmid-based quantitative competitive polymerase chain reaction.

PubMed

Shimizu, Eri; Kato, Hisashi; Nakagawa, Yuki; Kodama, Takashi; Futo, Satoshi; Minegishi, Yasutaka; Watanabe, Takahiro; Akiyama, Hiroshi; Teshima, Reiko; Furui, Satoshi; Hino, Akihiro; Kitta, Kazumi

2008-07-23

A novel type of quantitative competitive polymerase chain reaction (QC-PCR) system for the detection and quantification of the Roundup Ready soybean (RRS) was developed. This system was designed based on the advantage of a fully validated real-time PCR method used for the quantification of RRS in Japan. A plasmid was constructed as a competitor plasmid for the detection and quantification of genetically modified soy, RRS. The plasmid contained the construct-specific sequence of RRS and the taxon-specific sequence of lectin1 (Le1), and both had 21 bp oligonucleotide insertion in the sequences. The plasmid DNA was used as a reference molecule instead of ground seeds, which enabled us to precisely and stably adjust the copy number of targets. The present study demonstrated that the novel plasmid-based QC-PCR method could be a simple and feasible alternative to the real-time PCR method used for the quantification of genetically modified organism contents.

Four-hour quantitative real-time polymerase chain reaction-based comprehensive chromosome screening and accumulating evidence of accuracy, safety, predictive value, and clinical efficacy.

PubMed

Treff, Nathan R; Scott, Richard T

2013-03-15

Embryonic comprehensive chromosomal euploidy may represent a powerful biomarker to improve the success of IVF. However, there are a number of aneuploidy screening strategies to consider, including different technologic platforms with which to interrogate the embryonic DNA, and different embryonic developmental stages from which DNA can be analyzed. Although there are advantages and disadvantages associated with each strategy, a series of experiments producing evidence of accuracy, safety, clinical predictive value, and clinical efficacy indicate that trophectoderm biopsy and quantitative real-time polymerase chain reaction (qPCR)-based comprehensive chromosome screening (CCS) may represent a useful strategy to improve the success of IVF. This Biomarkers in Reproductive Medicine special issue review summarizes the accumulated experience with the development and clinical application of a 4-hour blastocyst qPCR-based CCS technology. Copyright © 2013 American Society for Reproductive Medicine. Published by Elsevier Inc. All rights reserved.

Rethinking fast and slow based on a critique of reaction-time reverse inference

PubMed Central

Krajbich, Ian; Bartling, Björn; Hare, Todd; Fehr, Ernst

2015-01-01

Do people intuitively favour certain actions over others? In some dual-process research, reaction-time (RT) data have been used to infer that certain choices are intuitive. However, the use of behavioural or biological measures to infer mental function, popularly known as ‘reverse inference', is problematic because it does not take into account other sources of variability in the data, such as discriminability of the choice options. Here we use two example data sets obtained from value-based choice experiments to demonstrate that, after controlling for discriminability (that is, strength-of-preference), there is no evidence that one type of choice is systematically faster than the other. Moreover, using specific variations of a prominent value-based choice experiment, we are able to predictably replicate, eliminate or reverse previously reported correlations between RT and selfishness. Thus, our findings shed crucial light on the use of RT in inferring mental processes and strongly caution against using RT differences as evidence favouring dual-process accounts. PMID:26135809

Rethinking fast and slow based on a critique of reaction-time reverse inference.

PubMed

Krajbich, Ian; Bartling, Björn; Hare, Todd; Fehr, Ernst

2015-07-02

Do people intuitively favour certain actions over others? In some dual-process research, reaction-time (RT) data have been used to infer that certain choices are intuitive. However, the use of behavioural or biological measures to infer mental function, popularly known as 'reverse inference', is problematic because it does not take into account other sources of variability in the data, such as discriminability of the choice options. Here we use two example data sets obtained from value-based choice experiments to demonstrate that, after controlling for discriminability (that is, strength-of-preference), there is no evidence that one type of choice is systematically faster than the other. Moreover, using specific variations of a prominent value-based choice experiment, we are able to predictably replicate, eliminate or reverse previously reported correlations between RT and selfishness. Thus, our findings shed crucial light on the use of RT in inferring mental processes and strongly caution against using RT differences as evidence favouring dual-process accounts.

No Evidence of Reaction Time Slowing in Autism Spectrum Disorder

ERIC Educational Resources Information Center

Ferraro, F. Richard

2016-01-01

A total of 32 studies comprising 238 simple reaction time and choice reaction time conditions were examined in individuals with autism spectrum disorder (n?=?964) and controls (n?=?1032). A Brinley plot/multiple regression analysis was performed on mean reaction times, regressing autism spectrum disorder performance onto the control performance as…

Trial-Level Regressor Modulation for Functional Magnetic Resonance Imaging Designs Requiring Strict Periodicity of Stimulus Presentations: Illustrated Using a Go/No-Go Task

PubMed Central

Motes, Michael A; Rao, Neena K; Shokri-Kojori, Ehsan; Chiang, Hsueh-Sheng; Kraut, Michael A; Hart, John

2017-01-01

Computer-based assessment of many cognitive processes (eg, anticipatory and response readiness processes) requires the use of invariant stimulus display times (SDT) and intertrial intervals (ITI). Although designs with invariant SDTs and ITIs have been used in functional magnetic resonance imaging (fMRI) research, such designs are problematic for fMRI studies because of collinearity issues. This study examined regressor modulation with trial-level reaction times (RT) as a method for improving signal detection in a go/no-go task with invariant SDTs and ITIs. The effects of modulating the go regressor were evaluated with respect to the detection of BOLD signal-change for the no-go condition. BOLD signal-change to no-go stimuli was examined when the go regressor was based on a (a) canonical hemodynamic response function (HRF), (b) RT-based amplitude-modulated (AM) HRF, and (c) RT-based amplitude and duration modulated (A&DM) HRF. Reaction time–based modulation reduced the collinearity between the go and no-go regressors, with A&DM producing the greatest reductions in correlations between the regressors, and greater reductions in the correlations between regressors were associated with longer mean RTs and greater RT variability. Reaction time–based modulation increased statistical power for detecting group-level no-go BOLD signal-change across a broad set of brain regions. The findings show the efficacy of using regressor modulation to increase power in detecting BOLD signal-change in fMRI studies in which circumstances dictate the use of temporally invariant stimulus presentations. PMID:29276390

Neuroticism Combined With Slower and More Variable Reaction Time: Synergistic Risk Factors for 7-Year Cognitive Decline in Females

PubMed Central

Shickle, Darren A.; Roberts, Beverly A.; Deary, Ian J.

2012-01-01

Objective. Among adults, slower and more variable reaction times are associated with worse cognitive function and increased mortality risk. Therefore, it is important to elucidate risk factors for reaction time change over the life course. Method. Data from the Health and Lifestyle Survey (HALS) were used to examine predictors of 7-year decline in reaction time (N = 4,260). Regression-derived factor scores were used to summarize general change across 4 reaction time variables: simple mean, 4-choice mean, simple variability, and 4-choice variability (53.52% of variance). Results. Age (B = .02, p < .001) and HALS1 baseline reaction time (B = −.10, p = .001) were significant risk factors for males (N = 1,899). In addition to these variables, in females (N = 2,361), neuroticism was significant and interacted synergistically with baseline reaction time (B = .06, p = .04). Adjustment for physiological variables explained the interaction with neuroticism, suggesting that candidate mechanisms had been identified. Discussion. A priority for future research is to replicate interactions between personality and reaction time in other samples and find specific mechanisms. Stratification of population data on cognitive health by personality and reaction time could improve strategies for identifying those at greater risk of cognitive decline. PMID:22367712

[Reaction time of drivers who caused road traffic accidents].

PubMed

Durić, Predrag; Filipović, Danka

2009-01-01

Human factor is the single cause of road traffic injuries in 57%, and together with other factors in more than 90% of all road traffic accidents. Human factor includes many aspects, where reaction time is very important. Thirty healthy drivers 28-40 y.o. with 50-500 km passed per week, having caused at least one road traffic accident in the last ten years were selected, provided they were not under the influence of alcohol and drugs during traffic accident. The same number of control were selected. Both cases and controls were tested to reaction time. We found statistically significant difference between car drivers who caused car accidents and those who did not in both simple and choice reaction times. Car drivers who caused road traffic accidents have longer reaction time (both simple and choice reaction time), but as the tasks were more complex, that difference was less visible. Since drivers involved in this study had introductory phase before measuring their reaction times, they faced with unpleasant sound when they made mistake, which forced them to be aware not to make a mistake in further tasks, so they showed longer reaction times. Measuring of reaction time seems to be important, and as we have showed they are different in drivers who have caused road traffic accidents and those who have do not.

Ignition delays, heats of combustion, and reaction rates of aluminum alkyl derivatives used as ignition and combustion enhancers for supersonic combustors

NASA Technical Reports Server (NTRS)

Ryan, T. W., III; Harlowe, W. W.; Schwab, S.

1992-01-01

The work was based on adapting an apparatus and procedure developed at Southwest Research Institute for rating the ignition quality of fuels for diesel engines. Aluminum alkyls and various Lewis-base adducts of these materials, both neat and mixed 50/50 with pure JP-10 hydrocarbon, were injected into the combustion bomb using a high-pressure injection system. The bomb was pre-charged with air that was set at various initial temperatures and pressures for constant oxygen density. The ignition delay times were determined for the test materials at these different initial conditions. The data are presented in absolute terms as well as comparisons with the parent alkyls. The relative heats of reaction of the various test materials were estimated based on a computation of the heat release, using the pressure data recorded during combustion in the bomb. In addition, the global reaction rates for each material were compared at a selected tmperature and pressure.

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

Kim, N.S.K.

In aqueous lysine-sucrose model systems, the effects of reaction time, pH and molar ratio were studied on the formation of non-enzymatic browning reaction (NBR) products. The extent of sucrose hydrolysis was measured and the antioxidant effect of NBR products on linoleic acid emulsions was examined. Nuclear magnetic resonance (NMR) spectra were obtained at various stages of browning. Sucrose produced NMR produces with lysine in an aqueous system at 100/sup 0/C. The C-13 NMR spectra indicated that the NBR started when sucrose and lysine were dissolved in water. The C-13 NMR spectra also showed that heating did not have an effectmore » on the gross composition of polymeric species. The absorbance at 480 nm of 0.75 M lysine-sucrose solution heated up to 6 hours increased with reaction times. The pH values of heated lysine-sucrose solution gradually decreased with reaction time. When 0.75 M sucrose or lysine solution was heated separately up to 6 hours, there were no changes in absorbance in pH. In the pH range of 3.52-6.35, higher absorbance was obtained from heated lysine-sucrose solution at acidic pH levels than at neutral pH levels. As the concentration of lysine and sucrose solution was increased, the absorbance increased. At longer reaction times or acidic pH levels, enhanced hydrolysis of sucrose to reducing sugars resulted in more NBR products. NBR products obtained at a longer reaction time, an acidic pH, and higher concentration of reactants showed a darker brown color and were effective in preventing the formation of peroxides. The oxygen uptake of linoleic acid emulsion having NBR products was smaller than that of linoleic acid emulsion without NBR products. Based on these results, it was concluded that sucrose may act as an antioxidant in processed foods containing both amino acids and lipids.« less

Etude des proprietes de surface et des proprietes rheologiques des melanges polymeres thermotropes

NASA Astrophysics Data System (ADS)

Tovar Hernandez, Maria Gabriela

We studied the surface and rheological properties of thermotropic liquid crystal polymers (TLCP) mixed with thermoplastics. We first investigated acid-base interactions in polymer component as a function of temperature, and could identified the many phase changes in TLCP. We found that acid-base interactions in TLCP decrease significantly with temperature, down to a point Tc where they become negligible. To our knowledge, it is the first time such observation is reported concerning TLCP. Acid-base interactions in the thermoplastics also vary with temperature, but they remain non-negligible, and reach a plateau at high temperature. In theory, one can obtain compatible blends between polymers A and B when their interaction parameters are both small and similar. The negligible acid-base parameter of TLCP at T > Tc should enhance the compatibility with thermoplastics. For that reason, we prepared the TLCP/thermoplastic blends at temperatures superior and inferior to Tc. We restricted our investigation to blends prepared in a Brabender Plasticorder in order to control the temperature in the mixing chamber and reduce the effects of TLCP domains deformation and reorientation. We prepared Vectra/polycarbonate blends, optimizing the drying conditions and the TLCP concentration. We optimized the drying conditions based on our previous results, finding that the transesterification reaction in presence of water happens at high temperature. Transesterification reaction was identified using infrared spectroscopy in the polymer components and in the blends. We found that this reaction occurring mainly between the ester groups in the polymer components. The product of this reaction, concentrated at the interfaces, has a remarkable effect on the blend morphology, similar to the one in compatible blend, and on its mechanical properties. To measure the effect of transesterification at the interfaces, we studied the linear viscoelasticity properties of Vectra/polycarbonate blend and their relation with their morphology. We found from the time variation of the elastic modulus at very low frequencies that the transesterification reaction was still occurring during rheological measurements. We observed coalescence of the dispersed phase droplets in all blends. Size of the droplets changed with the blend composition, the preparation temperature and the rheological characterization temperature. In addition, we compared Palierne (1990, 1991) and Lee-Park models when applied to Vectra/polycarbonate blends. We found that the Palierne model does not predict the rheological behavior of the blend, due to the mixture rule used in that model. Lee-Park model, using a different mixture rule, gives a good prediction of the linear viscoelastic properties. We succeeded in modeling the Vectra/polycarbonate rheological properties combining the characteristic relaxation times of the Palierne and Lee-Park models. Using this approach, we could clearly show that the decrease of the interfacial tension is due to the copolymer produced at the interface by transesterification reaction.

Determination of phosphorus fertilizer soil reactions by Raman and synchrotron infrared microspectroscopy.

PubMed

Vogel, Christian; Adam, Christian; Sekine, Ryo; Schiller, Tara; Lipiec, Ewelina; McNaughton, Don

2013-10-01

The reaction mechanisms of phosphate-bearing mineral phases from sewage sludge ash-based fertilizers in soil were determined by Raman and synchrotron infrared microspectroscopy. Different reaction mechanisms in wet soil were found for calcium and magnesium (pyro-) phosphates. Calcium orthophosphates were converted over time to hydroxyapatite. Conversely, different magnesium phosphates were transformed to trimagnesium phosphate. Since the magnesium phosphates are unable to form an apatite structure, the plant-available phosphorus remains in the soil, leading to better growth results observed in agricultural pot experiments. The pyrophosphates also reacted very differently. Calcium pyrophosphate is unreactive in soil. In contrast, magnesium pyrophosphate quickly formed plant-available dimagnesium phosphate.

Selective Formation of Secondary Amides via the Copper-Catalyzed Cross-Coupling of Alkylboronic Acids with Primary Amides

PubMed Central

Rossi, Steven A.; Shimkin, Kirk W.; Xu, Qun; Mori-Quiroz, Luis M.; Watson, Donald A.

2014-01-01

For the first time, a general catalytic procedure for the cross coupling of primary amides and alkylboronic acids is demonstrated. The key to the success of this reaction was the identification of a mild base (NaOSiMe3) and oxidant (di-tert-butyl peroxide) to promote the copper-catalyzed reaction in high yield. This transformation provides a facile, high-yielding method for the mono-alkylation of amides. PMID:23611591

Synthesis and properties of fatty acid starch esters.

PubMed

Winkler, Henning; Vorwerg, Waltraud; Wetzel, Hendrik

2013-10-15

Being completely bio-based, fatty acid starch esters (FASEs) are attractive materials that represent an alternative to crude oil-based plastics. In this study, two synthesis methods were compared in terms of their efficiency, toxicity and, especially, product solubility with starch laurate (C12) as model compound. Laurates (DS>2) were obtained through transesterification of fatty acid vinylesters in DMSO or reaction with fatty acid chlorides in pyridine. The latter lead to higher DS-values in a shorter reaction time. But due to the much better solubility of the products compared to lauroyl chloride esterified ones, vinylester-transesterification was preferred to optimize reaction parameters, where reaction time could be shortened to 2h. FASEs C6-C18 were also successfully prepared via transesterification. To determine the DS of the resulting starch laurates, the efficient ATR-IR method was compared with common methods (elementary analysis, (1)H NMR). Molar masses (Mw) of the highly soluble starch laurates were analyzed using SEC-MALLS (THF). High recovery rates (>80%) attest to the outstanding solubility of products obtained through transesterification, caused by a slight disintegration during synthesis. Particle size distributions (DLS) demonstrated stable dissolutions in CHCl3 of vinyl laurate esterified - contrary to lauroyl chloride esterified starch. For all highly soluble FASEs (C6-C18), formation of concentrated solutions (10 wt%) is feasible. Copyright © 2013 Elsevier Ltd. All rights reserved.

Propagation of Cutaneous Thermal Injury: A Mathematical Model

PubMed Central

Xue, Chuan; Chou, Ching-Shan; Kao, Chiu-Yen; Sen, Chandan K.; Friedman, Avner

2012-01-01

Cutaneous burn wounds represent a significant public health problem with 500,000 patients per year in the U.S. seeking medical attention. Immediately after skin burn injury, the volume of the wound burn expands due to a cascade of chemical reactions, including lipid peroxidation chain reactions. Based on these chemical reactions, the present paper develops for the first time a three-dimensional mathematical model to quantify the propagation of tissue damage within 12 hours post initial burn. We use the model to investigate the effect of supplemental antioxidant vitamin E for stopping the propagation. We show, for example, that if the production rate of vitamin E is increased, post burn, by five times the natural production in a healthy tissue, then this would slow down the lipid peroxide propagation by at least 50%. Our model is formulated in terms of differential equations, and sensitivity analysis is performed on the parameters to ensure the robustness of the results. PMID:22211391

A green recyclable SO(3)H-carbon catalyst derived from glycerol for the production of biodiesel from FFA-containing karanja (Pongamia glabra) oil in a single step.

PubMed

Prabhavathi Devi, B L A; Vijai Kumar Reddy, T; Vijaya Lakshmi, K; Prasad, R B N

2014-02-01

Simultaneous esterification and transesterification method is employed for the preparation of biodiesel from 7.5% free fatty acid (FFA) containing karanja (Pongamia glabra) oil using water resistant and reusable carbon-based solid acid catalyst derived from glycerol in a single step. The optimum reaction parameters for obtaining biodiesel in >99% yield by simultaneous esterification and transesterification are: methanol (1:45 mole ratio of oil), catalyst 20wt.% of oil, temperature 160°C and reaction time of 4h. After the reaction, the catalyst was easily recovered by filtration and reused for five times with out any deactivation under optimized conditions. This single-step process could be a potential route for biodiesel production from high FFA containing oils by simplifying the procedure and reducing costs and effluent generation. Copyright © 2013 Elsevier Ltd. All rights reserved.

Event specific qualitative and quantitative polymerase chain reaction detection of genetically modified MON863 maize based on the 5'-transgene integration sequence.

PubMed

Yang, Litao; Xu, Songci; Pan, Aihu; Yin, Changsong; Zhang, Kewei; Wang, Zhenying; Zhou, Zhigang; Zhang, Dabing

2005-11-30

Because of the genetically modified organisms (GMOs) labeling policies issued in many countries and areas, polymerase chain reaction (PCR) methods were developed for the execution of GMO labeling policies, such as screening, gene specific, construct specific, and event specific PCR detection methods, which have become a mainstay of GMOs detection. The event specific PCR detection method is the primary trend in GMOs detection because of its high specificity based on the flanking sequence of the exogenous integrant. This genetically modified maize, MON863, contains a Cry3Bb1 coding sequence that produces a protein with enhanced insecticidal activity against the coleopteran pest, corn rootworm. In this study, the 5'-integration junction sequence between the host plant DNA and the integrated gene construct of the genetically modified maize MON863 was revealed by means of thermal asymmetric interlaced-PCR, and the specific PCR primers and TaqMan probe were designed based upon the revealed 5'-integration junction sequence; the conventional qualitative PCR and quantitative TaqMan real-time PCR detection methods employing these primers and probes were successfully developed. In conventional qualitative PCR assay, the limit of detection (LOD) was 0.1% for MON863 in 100 ng of maize genomic DNA for one reaction. In the quantitative TaqMan real-time PCR assay, the LOD and the limit of quantification were eight and 80 haploid genome copies, respectively. In addition, three mixed maize samples with known MON863 contents were detected using the established real-time PCR systems, and the ideal results indicated that the established event specific real-time PCR detection systems were reliable, sensitive, and accurate.

Kinetics of patulin degradation in model solution, apple cider and apple juice by ultraviolet radiation.

PubMed

Zhu, Yan; Koutchma, Tatiana; Warriner, Keith; Shao, Suqin; Zhou, Ting

2013-08-01

Patulin is a mycotoxin produced by a wide range of molds involved in fruit spoilage, most commonly by Penicillium expansum and is a health concern for both consumers and manufacturers. The current study evaluated feasibility of monochromatic ultraviolet (UV) radiation at 253.7 nm as a possible commercial application for the reduction of patulin in fresh apple cider and juice. The R-52G MINERALIGHT® UV bench top lamp was used for patulin destruction. It was shown that 56.5%, 87.5%, 94.8% and 98.6% reduction of patulin can be achieved, respectively, in the model solution, apple cider, apple juice without ascorbic acid addition and apple juice with ascorbic acid addition in 2-mm thickness sample initially spiked by 1 mg·L(-1) of patulin after UV exposure for 40 min at UV irradiance of 3.00 mW·cm(-2). A mathematic model to compare the degradation rate and effective UV dose was developed. The effective UV doses that were directly absorbed by patulin for photochemical reaction were 430, 674, 724 and 763 mJ·cm(-3), respectively. The fluence-based decimal reduction time was estimated to 309.3, 31.3, 28.9 and 5.1 mW·cm(-2)·min, respectively, in four media mentioned above. The degradation of patulin followed the first-order reaction model. The time-based and fluence-based reaction rate constants were determined to predict patulin degradation. The time-based reaction rate constant of samples treated in dynamic regime with constant stirring (model solution: 2.95E-4 s(-1), juice: 4.31E-4 s(-1)) were significantly higher than samples treated in static regime (model solution: 2.79E-4 s(-1), juice: 3.49E-4 s(-1), p < 0.05) when applied UV irradiance and sample thickness were consistent. The reaction rate constant of patulin degradation in apple juice was significantly higher than model solution (p < 0.05). Although further investigations are still needed, the results of this study demonstrated that UV radiation may be an effective method for treating patulin-containing apple cider and juice.

Single-digit Arabic numbers do not automatically activate magnitude representations in adults or in children: Evidence from the symbolic same–different task☆

PubMed Central

Wong, Becky; Szücs, Dénes

2013-01-01

We investigated whether the mere presentation of single-digit Arabic numbers activates their magnitude representations using a visually-presented symbolic same–different task for 20 adults and 15 children. Participants saw two single-digit Arabic numbers on a screen and judged whether the numbers were the same or different. We examined whether reaction time in this task was primarily driven by (objective or subjective) perceptual similarity, or by the numerical difference between the two digits. We reasoned that, if Arabic numbers automatically activate magnitude representations, a numerical function would best predict reaction time; but if Arabic numbers do not automatically activate magnitude representations, a perceptual function would best predict reaction time. Linear regressions revealed that a perceptual function, specifically, subjective visual similarity, was the best and only significant predictor of reaction time in adults and in children. These data strongly suggest that, in this task, single-digit Arabic numbers do not necessarily automatically activate magnitude representations in adults or in children. As the first study to date to explicitly study the developmental importance of perceptual factors in the symbolic same–different task, we found no significant differences between adults and children in their reliance on perceptual information in this task. Based on our findings, we propose that visual properties may play a key role in symbolic number judgements. PMID:24076332

Virtual Instrument for Determining Rate Constant of Second-Order Reaction by pX Based on LabVIEW 8.0.

PubMed

Meng, Hu; Li, Jiang-Yuan; Tang, Yong-Huai

2009-01-01

The virtual instrument system based on LabVIEW 8.0 for ion analyzer which can measure and analyze ion concentrations in solution is developed and comprises homemade conditioning circuit, data acquiring board, and computer. It can calibrate slope, temperature, and positioning automatically. When applied to determine the reaction rate constant by pX, it achieved live acquiring, real-time displaying, automatical processing of testing data, generating the report of results; and other functions. This method simplifies the experimental operation greatly, avoids complicated procedures of manual processing data and personal error, and improves veracity and repeatability of the experiment results.

Reaction Event Counting Statistics of Biopolymer Reaction Systems with Dynamic Heterogeneity.

PubMed

Lim, Yu Rim; Park, Seong Jun; Park, Bo Jung; Cao, Jianshu; Silbey, Robert J; Sung, Jaeyoung

2012-04-10

We investigate the reaction event counting statistics (RECS) of an elementary biopolymer reaction in which the rate coefficient is dependent on states of the biopolymer and the surrounding environment and discover a universal kinetic phase transition in the RECS of the reaction system with dynamic heterogeneity. From an exact analysis for a general model of elementary biopolymer reactions, we find that the variance in the number of reaction events is dependent on the square of the mean number of the reaction events when the size of measurement time is small on the relaxation time scale of rate coefficient fluctuations, which does not conform to renewal statistics. On the other hand, when the size of the measurement time interval is much greater than the relaxation time of rate coefficient fluctuations, the variance becomes linearly proportional to the mean reaction number in accordance with renewal statistics. Gillespie's stochastic simulation method is generalized for the reaction system with a rate coefficient fluctuation. The simulation results confirm the correctness of the analytic results for the time dependent mean and variance of the reaction event number distribution. On the basis of the obtained results, we propose a method of quantitative analysis for the reaction event counting statistics of reaction systems with rate coefficient fluctuations, which enables one to extract information about the magnitude and the relaxation times of the fluctuating reaction rate coefficient, without a bias that can be introduced by assuming a particular kinetic model of conformational dynamics and the conformation dependent reactivity. An exact relationship is established between a higher moment of the reaction event number distribution and the multitime correlation of the reaction rate for the reaction system with a nonequilibrium initial state distribution as well as for the system with the equilibrium initial state distribution.

Inquiry-Based Experiments for Large-Scale Introduction to PCR and Restriction Enzyme Digests

ERIC Educational Resources Information Center

Johanson, Kelly E.; Watt, Terry J.

2015-01-01

Polymerase chain reaction and restriction endonuclease digest are important techniques that should be included in all Biochemistry and Molecular Biology laboratory curriculums. These techniques are frequently taught at an advanced level, requiring many hours of student and faculty time. Here we present two inquiry-based experiments that are…

Action or Reaction, Learning or Display: Interactional Development and Usage-Based Data

ERIC Educational Resources Information Center

Huth, Thorsten

2013-01-01

This paper investigates how instances of language use can serve as analytic anchors for insight into interactional development over time. I present a usage-based, longitudinal study of multi-turn sequences underlying telephone openings in order to specify if and to whom "language learning" may be relevantly ascribed. Two successive…

A fluorescence high throughput screening method for the detection of reactive electrophiles as potential skin sensitizers.

PubMed

Avonto, Cristina; Chittiboyina, Amar G; Rua, Diego; Khan, Ikhlas A

2015-12-01

Skin sensitization is an important toxicological end-point in the risk assessment of chemical allergens. Because of the complexity of the biological mechanisms associated with skin sensitization, integrated approaches combining different chemical, biological and in silico methods are recommended to replace conventional animal tests. Chemical methods are intended to characterize the potential of a sensitizer to induce earlier molecular initiating events. The presence of an electrophilic mechanistic domain is considered one of the essential chemical features to covalently bind to the biological target and induce further haptenation processes. Current in chemico assays rely on the quantification of unreacted model nucleophiles after incubation with the candidate sensitizer. In the current study, a new fluorescence-based method, 'HTS-DCYA assay', is proposed. The assay aims at the identification of reactive electrophiles based on their chemical reactivity toward a model fluorescent thiol. The reaction workflow enabled the development of a High Throughput Screening (HTS) method to directly quantify the reaction adducts. The reaction conditions have been optimized to minimize solubility issues, oxidative side reactions and increase the throughput of the assay while minimizing the reaction time, which are common issues with existing methods. Thirty-six chemicals previously classified with LLNA, DPRA or KeratinoSens™ were tested as a proof of concept. Preliminary results gave an estimated 82% accuracy, 78% sensitivity, 90% specificity, comparable to other in chemico methods such as Cys-DPRA. In addition to validated chemicals, six natural products were analyzed and a prediction of their sensitization potential is presented for the first time. Copyright © 2015 Elsevier Inc. All rights reserved.

Binary counting with chemical reactions.

PubMed

Kharam, Aleksandra; Jiang, Hua; Riedel, Marc; Parhi, Keshab

2011-01-01

This paper describes a scheme for implementing a binary counter with chemical reactions. The value of the counter is encoded by logical values of "0" and "1" that correspond to the absence and presence of specific molecular types, respectively. It is incremented when molecules of a trigger type are injected. Synchronization is achieved with reactions that produce a sustained three-phase oscillation. This oscillation plays a role analogous to a clock signal in digital electronics. Quantities are transferred between molecular types in different phases of the oscillation. Unlike all previous schemes for chemical computation, this scheme is dependent only on coarse rate categories for the reactions ("fast" and "slow"). Given such categories, the computation is exact and independent of the specific reaction rates. Although conceptual for the time being, the methodology has potential applications in domains of synthetic biology such as biochemical sensing and drug delivery. We are exploring DNA-based computation via strand displacement as a possible experimental chassis.

Direct and Efficient Dehydrogenation of Tetrahydroquinolines and Primary Amines Using Corona Discharge Generated on Ambient Hydrophobic Paper Substrate.

PubMed

Davis, Kathryn M; Badu-Tawiah, Abraham K

2017-04-01

The exposure of an aqueous-based liquid drop containing amines and graphite particles to plasma generated by a corona discharge results in heterogeneous aerobic dehydrogenation reactions. This green oxidation reaction occurring in ambient air afforded the corresponding quinolines and nitriles from tetrahydroquinolines and primary amines, respectively, at >96% yields in less than 2 min of reaction time. The accelerated dehydrogenation reactions occurred on the surface of a low energy hydrophobic paper, which served both as container for holding the reacting liquid drop and as a medium for achieving paper spray ionization of reaction products for subsequent characterization by ambient mass spectrometry. Control experiments indicate superoxide anions (O 2 •- ) are the main reactive species; the presence of graphite particles introduced heterogeneous surface effects, and enabled the efficient sampling of the plasma into the grounded analyte droplet solution. Graphical Abstract ᅟ.

Study on monostable and bistable reaction-diffusion equations by iteration of travelling wave maps

NASA Astrophysics Data System (ADS)

Yi, Taishan; Chen, Yuming

2017-12-01

In this paper, based on the iterative properties of travelling wave maps, we develop a new method to obtain spreading speeds and asymptotic propagation for monostable and bistable reaction-diffusion equations. Precisely, for Dirichlet problems of monostable reaction-diffusion equations on the half line, by making links between travelling wave maps and integral operators associated with the Dirichlet diffusion kernel (the latter is NOT invariant under translation), we obtain some iteration properties of the Dirichlet diffusion and some a priori estimates on nontrivial solutions of Dirichlet problems under travelling wave transformation. We then provide the asymptotic behavior of nontrivial solutions in the space-time region for Dirichlet problems. These enable us to develop a unified method to obtain results on heterogeneous steady states, travelling waves, spreading speeds, and asymptotic spreading behavior for Dirichlet problem of monostable reaction-diffusion equations on R+ as well as of monostable/bistable reaction-diffusion equations on R.

Direct and Efficient Dehydrogenation of Tetrahydroquinolines and Primary Amines Using Corona Discharge Generated on Ambient Hydrophobic Paper Substrate

NASA Astrophysics Data System (ADS)

Davis, Kathryn M.; Badu-Tawiah, Abraham K.

2017-04-01

The exposure of an aqueous-based liquid drop containing amines and graphite particles to plasma generated by a corona discharge results in heterogeneous aerobic dehydrogenation reactions. This green oxidation reaction occurring in ambient air afforded the corresponding quinolines and nitriles from tetrahydroquinolines and primary amines, respectively, at >96% yields in less than 2 min of reaction time. The accelerated dehydrogenation reactions occurred on the surface of a low energy hydrophobic paper, which served both as container for holding the reacting liquid drop and as a medium for achieving paper spray ionization of reaction products for subsequent characterization by ambient mass spectrometry. Control experiments indicate superoxide anions (O2 •-) are the main reactive species; the presence of graphite particles introduced heterogeneous surface effects, and enabled the efficient sampling of the plasma into the grounded analyte droplet solution.

Chemical clocks, oscillations, and other temporal effects in analytical chemistry: oddity or viable approach?

PubMed

Prabhu, Gurpur Rakesh D; Witek, Henryk A; Urban, Pawel L

2018-05-31

Most analytical methods are based on "analogue" inputs from sensors of light, electric potentials, or currents. The signals obtained by such sensors are processed using certain calibration functions to determine concentrations of the target analytes. The signal readouts are normally done after an optimised and fixed time period, during which an assay mixture is incubated. This minireview covers another-and somewhat unusual-analytical strategy, which relies on the measurement of time interval between the occurrences of two distinguishable states in the assay reaction. These states manifest themselves via abrupt changes in the properties of the assay mixture (e.g. change of colour, appearance or disappearance of luminescence, change in pH, variations in optical activity or mechanical properties). In some cases, a correlation between the time of appearance/disappearance of a given property and the analyte concentration can be also observed. An example of an assay based on time measurement is an oscillating reaction, in which the period of oscillations is linked to the concentration of the target analyte. A number of chemo-chronometric assays, relying on the existing (bio)transformations or artificially designed reactions, were disclosed in the past few years. They are very attractive from the fundamental point of view but-so far-only few of them have be validated and used to address real-world problems. Then, can chemo-chronometric assays become a practical tool for chemical analysis? Is there a need for further development of such assays? We are aiming to answer these questions.

Isothermal titration calorimetry in nanoliter droplets with subsecond time constants.

PubMed

Lubbers, Brad; Baudenbacher, Franz

2011-10-15

We reduced the reaction volume in microfabricated suspended-membrane titration calorimeters to nanoliter droplets and improved the sensitivities to below a nanowatt with time constants of around 100 ms. The device performance was characterized using exothermic acid-base neutralizations and a detailed numerical model. The finite element based numerical model allowed us to determine the sensitivities within 1% and the temporal dynamics of the temperature rise in neutralization reactions as a function of droplet size. The model was used to determine the optimum calorimeter design (membrane size and thickness, junction area, and thermopile thickness) and sensitivities for sample volumes of 1 nL for silicon nitride and polymer membranes. We obtained a maximum sensitivity of 153 pW/(Hz)(1/2) for a 1 μm SiN membrane and 79 pW/(Hz)(1/2) for a 1 μm polymer membrane. The time constant of the calorimeter system was determined experimentally using a pulsed laser to increase the temperature of nanoliter sample volumes. For a 2.5 nanoliter sample volume, we experimentally determined a noise equivalent power of 500 pW/(Hz)(1/2) and a 1/e time constant of 110 ms for a modified commercially available infrared sensor with a thin-film thermopile. Furthermore, we demonstrated detection of 1.4 nJ reaction energies from injection of 25 pL of 1 mM HCl into a 2.5 nL droplet of 1 mM NaOH. © 2011 American Chemical Society

Temperature-dependent ozone chemiluminescence: A new approach for hydrocarbon monitoring

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

Marley, N.; Gaffney, J.

1996-12-31

Ozone chemiluminescent reactions have been used for some time to detect oxides of nitrogen, ozone, and olefins in air quality studies. Current procedures use non-methane hydrocarbon analyzers based on the flame ionization detector (FID), which quantitate total non-methane hydrocarbons but do not differentiate between the wide variety of volatile organic classes and oxygenates. The other methodology that has been used, gas chromatography/mass spectroscopy (GC/MS), can measure a variety of individual hydrocarbon species and classes, but it is costly, time-consuming, and labor intensive and is not amenable to real-time measurements. Presented here is preliminary research aimed at the development of anmore » alternative to FID and GC/MS: the ozone chemiluminescent detector (OCD) for measurement of a variety of hydrocarbon species and classes by use of the temperature dependence of ozone chemiluminescent reactions. Responses for various hydrocarbon classes obtained with an OCD operated at 170 C or the FID were compared. The results indicate that the OCD detector responds like a total carbon detector at this temperature, with sensitivities 10-100 times higher than those of a FID. Use of the temperature dependence of the chemiluminescent reaction and prereactors will apparently make a real-time hydrocarbon analyzer based on this approach feasible for determination of high-, moderate-, and low-reactivity hydrocarbon levels in ambient air. The OCD approach may be very useful in determining oxygenate emissions from motor vehicles, particularly alternative fuels. The OCD may also be useful in monitoring of ambient air for natural hydrocarbon emissions.« less

Heterocyclic Schiff bases as non toxic antioxidants: Solvent effect, structure activity relationship and mechanism of action

NASA Astrophysics Data System (ADS)

Shanty, Angamaly Antony; Mohanan, Puzhavoorparambil Velayudhan

2018-03-01

Phenolic heterocyclic imine based Schiff bases from Thiophene-2-carboxaldehyde and Pyrrole-2-carboxaldehyde were synthesized and characterized as novel antioxidants. The solvent effects of these Schiff bases were determined and compared with standard antioxidants, BHA employing DPPH assay and ABTS assay. Fixed reaction time and Steady state measurement were used for study. IC50 and EC50 were calculated. Structure-activity relationship revealed that the electron donating group in the phenolic ring increases the activity where as the electron withdrawing moiety decreases the activity. The Schiff base derivatives showed antioxidant property by two different pathways namely SPLET and HAT mechanisms in DPPH assay. While in ABTS method, the reaction between ABTS radical and Schiff bases involves electron transfer followed by proton transfer (ET-PT) mechanism. The cytotoxicity of these compounds has been evaluated by MTT assay. The results showed that all these compounds are non toxic in nature.

Graphene-oxide-supported CuAl and CoAl layered double hydroxides as enhanced catalysts for carbon-carbon coupling via Ullmann reaction

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

Ahmed, Nesreen S.; Surface Chemistry and Catalytic Studies Group, King Abdulaziz University; Menzel, Robert

Two efficient catalyst based on CuAl and CoAl layered double hydroxides (LDHs) supported on graphene oxide (GO) for the carbon-carbon coupling (Classic Ullmann Homocoupling Reaction) are reported. The pure and hybrid materials were synthesised by direct precipitation of the LDH nanoparticles onto GO, followed by a chemical, structural and physical characterisation by electron microscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), surface area measurements and X-ray photoelectron spectroscopy (XPS). The GO-supported and unsupported CuAl-LDH and CoAl-LDH hybrids were tested over the Classic Ullman Homocoupling Reaction of iodobenzene. In the current study CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%,more » respectively) at very short reaction times (25 min). GO provides a light-weight, charge complementary and two-dimensional material that interacts effectively with the 2D LDHs, in turn enhancing the stability of LDH. After 5 re-use cycles, the catalytic activity of the LDH/GO hybrid is up to 2 times higher than for the unsupported LDH. - Graphical abstract: CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%, respectively) at very short reaction times (25 min). GO provides a light-weight, charge complementary, two-dimensional material that interacts effectively with the 2D LDHs, in turn enhancing the stability of LDH. - Highlights: • CuAl LDH/GO and CoAl LDH/GO hybrid materials with different LDH compositions were prepared. • Hybrids were fully characterised and their catalytic efficiency over the Classic Ullman Reaction was studied. • CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%, respectively) in 25 min reaction times. • GO provides a light-weight, charge complementary, two-dimensional material that interacts effectively with the 2D LDHs. • After 5 re-use cycles, the catalytic activity of the LDH/GO hybrid is up to 2 times higher than for the unsupported LDH.« less

Assessing Cognitive Performance in Badminton Players: A Reproducibility and Validity Study

PubMed Central

van de Water, Tanja; Faber, Irene; Elferink-Gemser, Marije

2017-01-01

Abstract Fast reaction and good inhibitory control are associated with elite sports performance. To evaluate the reproducibility and validity of a newly developed Badminton Reaction Inhibition Test (BRIT), fifteen elite (25 ± 4 years) and nine non-elite (24 ± 4 years) Dutch male badminton players participated in the study. The BRIT measured four components: domain-general reaction time, badminton-specific reaction time, domain-general inhibitory control and badminton-specific inhibitory control. Five participants were retested within three weeks on the badminton-specific components. Reproducibility was acceptable for badminton-specific reaction time (ICC = 0.626, CV = 6%) and for badminton-specific inhibitory control (ICC = 0.317, CV = 13%). Good construct validity was shown for badminton-specific reaction time discriminating between elite and non-elite players (F = 6.650, p < 0.05). Elite players did not outscore non-elite players on domain-general reaction time nor on both components of inhibitory control (p > 0.05). Concurrent validity for domain-general reaction time was good, as it was associated with a national ranking for elite (p = 0.70, p < 0.01) and non-elite (p = 0.70, p < 0.05) players. No relationship was found between the national ranking and badminton-specific reaction time, nor both components of inhibitory control (p > 0.05). In conclusion, reproducibility and validity of inhibitory control assessment was not confirmed, however, the BRIT appears a reproducible and valid measure of reaction time in badminton players. Reaction time measured with the BRIT may provide input for training programs aiming to improve badminton players’ performance. PMID:28210347

Assessing Cognitive Performance in Badminton Players: A Reproducibility and Validity Study.

PubMed

van de Water, Tanja; Huijgen, Barbara; Faber, Irene; Elferink-Gemser, Marije

2017-01-01

Fast reaction and good inhibitory control are associated with elite sports performance. To evaluate the reproducibility and validity of a newly developed Badminton Reaction Inhibition Test (BRIT), fifteen elite (25 ± 4 years) and nine non-elite (24 ± 4 years) Dutch male badminton players participated in the study. The BRIT measured four components: domain-general reaction time, badminton-specific reaction time, domain-general inhibitory control and badminton-specific inhibitory control. Five participants were retested within three weeks on the badminton-specific components. Reproducibility was acceptable for badminton-specific reaction time (ICC = 0.626, CV = 6%) and for badminton-specific inhibitory control (ICC = 0.317, CV = 13%). Good construct validity was shown for badminton-specific reaction time discriminating between elite and non-elite players (F = 6.650, p < 0.05). Elite players did not outscore non-elite players on domain-general reaction time nor on both components of inhibitory control (p > 0.05). Concurrent validity for domain-general reaction time was good, as it was associated with a national ranking for elite (p = 0.70, p < 0.01) and non-elite (p = 0.70, p < 0.05) players. No relationship was found between the national ranking and badminton-specific reaction time, nor both components of inhibitory control (p > 0.05). In conclusion, reproducibility and validity of inhibitory control assessment was not confirmed, however, the BRIT appears a reproducible and valid measure of reaction time in badminton players. Reaction time measured with the BRIT may provide input for training programs aiming to improve badminton players' performance.

Development of a high-speed real-time PCR system for rapid and precise nucleotide recognition

NASA Astrophysics Data System (ADS)

Terazono, Hideyuki; Takei, Hiroyuki; Hattori, Akihiro; Yasuda, Kenji

2010-04-01

Polymerase chain reaction (PCR) is a common method used to create copies of a specific target region of a DNA sequence and to produce large quantities of DNA. A few DNA molecules, which act as templates, are rapidly amplified by PCR into many billions of copies. PCR is a key technology in genome-based biological analysis, revolutionizing many life science fields such as medical diagnostics, food safety monitoring, and countermeasures against bioterrorism. Thus, many applications have been developed with the thermal cycling. For these PCR applications, one of the most important key factors is reduction in the data acquisition time. To reduce the acquisition time, it is necessary to decrease the temperature transition time between the high and low ends as much as possible. We have developed a novel rapid real-time PCR system based on rapid exchange of media maintained at different temperatures. This system consists of two thermal reservoirs and a reaction chamber for PCR observation. The temperature transition was achieved within 0.3 sec, and good thermal stability was achieved during thermal cycling with rapid exchange of circulating media. This system allows rigorous optimization of the temperatures required for each stage of the PCR processes. Resulting amplicons were confirmed by electrophoresis. Using the system, rapid DNA amplification was accomplished within 3.5 min, including initial heating and complete 50 PCR cycles. It clearly shows that the device could allow us faster temperature switching than the conventional conduction-based heating systems based on Peltier heating/cooling.

Effect of Reaction Developing Training on Audio-Visual Feet Reaction Time in Wrestlers

ERIC Educational Resources Information Center

Kaya, Mustafa

2016-01-01

Reaction time is one of the most determinative elements for a successful sports performance. The purpose of this study was to investigate the effect of 12-week feet reaction developing trainings upon feet reaction time of females at 11-13 age interval. Volunteer sportsmen between 11 and 13 age interval who were active in Tokat Provincial…

The time course of corticospinal excitability during a simple reaction time task.

PubMed

Kennefick, Michael; Maslovat, Dana; Carlsen, Anthony N

2014-01-01

The production of movement in a simple reaction time task can be separated into two time periods: the foreperiod, which is thought to include preparatory processes, and the reaction time interval, which includes initiation processes. To better understand these processes, transcranial magnetic stimulation has been used to probe corticospinal excitability at various time points during response preparation and initiation. Previous research has shown that excitability decreases prior to the "go" stimulus and increases following the "go"; however these two time frames have been examined independently. The purpose of this study was to measure changes in CE during both the foreperiod and reaction time interval in a single experiment, relative to a resting baseline level. Participants performed a button press movement in a simple reaction time task and excitability was measured during rest, the foreperiod, and the reaction time interval. Results indicated that during the foreperiod, excitability levels quickly increased from baseline with the presentation of the warning signal, followed by a period of stable excitability leading up to the "go" signal, and finally a rapid increase in excitability during the reaction time interval. This excitability time course is consistent with neural activation models that describe movement preparation and response initiation.

Kinetics of non-catalyzed hydrolysis of tannin in high temperature liquid water*

PubMed Central

Lu, Li-li; Lu, Xiu-yang; Ma, Nan

2008-01-01

High temperature liquid water (HTLW) has drawn increasing attention as an environmentally benign medium for organic chemical reactions, especially acid-/base-catalyzed reactions. Non-catalyzed hydrolyses of gallotannin and tara tannin in HTLW for the simultaneous preparation of gallic acid (GA) and pyrogallol (PY) are under investigation in our laboratory. In this study, the hydrolysis kinetics of gallotannin and tara tannin were determined. The reaction is indicated to be a typical consecutive first-order one in which GA has formed as a main intermediate and PY as the final product. Selective decomposition of tannin in HTLW was proved to be possible by adjusting reaction temperature and time. The present results provide an important basic data and reference for the green preparation of GA and PY. PMID:18500780

Electron and Ion Reactions in Molecular Solids: from astrochemistry to radiobiology

NASA Astrophysics Data System (ADS)

Huels, Michael A.

2001-05-01

Wherever ionizing radiation interacts with matter, it initiates reaction cascades involving ions, radicals, and ballistic secondary electrons; these reactions occur on fs time-scales, and may lead to substantial physical and chemical modifications of a medium. Here I present measurements of 0-80 eV electron and ion reactions in condensed films ranging from simple to complex, and astrophysical to biological in nature. Targets contain either: small molecules, hydrocarbons of increasing complexity (incl. bases, sugars, single/double stranded DNA), molecules on rare gas matrices, or mixed cryogenic films resembling astrophysical or planetary surface ices containing O2, H2O, methane, and aromatic hydrocarbons. The basic electron or ion reaction mechanisms and pathways are found to be fundamentally universal, but are modulated by the physical and chemical nature of the medium; depending on the latter, a reaction cascade may lead to different end-points, e.g. a decrease in molecular complexity via molecular fragmentations, or increases in complexity via secondary ion collision induced synthesis of larger molecules in hydrocarbon rich surface ices.

The behavior of nanothermite reaction based on Bi2O3/Al

NASA Astrophysics Data System (ADS)

Wang, L.; Luss, D.; Martirosyan, K. S.

2011-10-01

We studied the impact of aluminum particle size and the thickness of surrounding alumina layer on the dynamic pressure discharge of nanothermite reactions in the Bi2O3/Al system. A pressure discharge from 9 to 13 MPa was generated using as-synthesized Bi2O3 nano-particles produced by combustion synthesis and Al nanoparticles with size from 3 μm to 100 nm. The maximum reaction temperature was measured to be ˜2700 °C. The estimated activation energy of the reaction was 45 kJ/mol. A very large (several orders of magnitude) difference existed between the rate of the pressure pulse release by nanothermite reactions and by thermite reactions with large aluminum particles. The maximum observed pressurization rate was 3200 GPa/s. The time needed to reach the peak pressure was 0.01 ms and 100 ms for aluminum particles with diameter of 100 nm and 70 microns, respectively. The discharge pressure was a monotonic decreasing function of the thickness of the surrounding alumina layer.

Intraindividual variability in reaction time predicts cognitive outcomes 5 years later.

PubMed

Bielak, Allison A M; Hultsch, David F; Strauss, Esther; Macdonald, Stuart W S; Hunter, Michael A

2010-11-01

Building on results suggesting that intraindividual variability in reaction time (inconsistency) is highly sensitive to even subtle changes in cognitive ability, this study addressed the capacity of inconsistency to predict change in cognitive status (i.e., cognitive impairment, no dementia [CIND] classification) and attrition 5 years later. Two hundred twelve community-dwelling older adults, initially aged 64-92 years, remained in the study after 5 years. Inconsistency was calculated from baseline reaction time performance. Participants were assigned to groups on the basis of their fluctuations in CIND classification over time. Logistic and Cox regressions were used. Baseline inconsistency significantly distinguished among those who remained or transitioned into CIND over the 5 years and those who were consistently intact (e.g., stable intact vs. stable CIND, Wald (1) = 7.91, p < .01, Exp(β) = 1.49). Average level of inconsistency over time was also predictive of study attrition, for example, Wald (1) = 11.31, p < .01, Exp(β) = 1.24. For both outcomes, greater inconsistency was associated with a greater likelihood of being in a maladaptive group 5 years later. Variability based on moderately cognitively challenging tasks appeared to be particularly sensitive to longitudinal changes in cognitive ability. Mean rate of responding was a comparable predictor of change in most instances, but individuals were at greater relative risk of being in a maladaptive outcome group if they were more inconsistent rather than if they were slower in responding. Implications for the potential utility of intraindividual variability in reaction time as an early marker of cognitive decline are discussed. (c) 2010 APA, all rights reserved

Airfoil sampling of a pulsed Laval beam with tunable vacuum ultraviolet synchrotron ionization quadrupole mass spectrometry: application to low-temperature kinetics and product detection.

PubMed

Soorkia, Satchin; Liu, Chen-Lin; Savee, John D; Ferrell, Sarah J; Leone, Stephen R; Wilson, Kevin R

2011-12-01

A new pulsed Laval nozzle apparatus with vacuum ultraviolet (VUV) synchrotron photoionization quadrupole mass spectrometry is constructed to study low-temperature radical-neutral chemical reactions of importance for modeling the atmosphere of Titan and the outer planets. A design for the sampling geometry of a pulsed Laval nozzle expansion has been developed that operates successfully for the determination of rate coefficients by time-resolved mass spectrometry. The new concept employs airfoil sampling of the collimated expansion with excellent sampling throughput. Time-resolved profiles of the high Mach number gas flow obtained by photoionization signals show that perturbation of the collimated expansion by the airfoil is negligible. The reaction of C(2)H with C(2)H(2) is studied at 70 K as a proof-of-principle result for both low-temperature rate coefficient measurements and product identification based on the photoionization spectrum of the reaction product versus VUV photon energy. This approach can be used to provide new insights into reaction mechanisms occurring at kinetic rates close to the collision-determined limit.

[Characteristics and mechanism of sodium removal by the synergistic action of flue gas and waste solid].

PubMed

Yi, Yuan-Rong; Han, Min-Fang

2012-07-01

The carbon dioxide (CO2) in flue gas was used to remove the sodium in the red mud (RM) , a kind of alkaline solid waste generated during alumina production. The reaction characteristics and mechanism of sodium removal by the synergistic action of CO2 and RM were studied with different medium pH, reaction time and temperature. It was demonstrated that the remove of sodium by RM was actually the result of the synergistic action of sodium-based solid waste in RM with the CO2-H2O and OH(-)-CO2 systems. The sodium removal efficiency was correlated with pH, reaction temperature and time. The characteristics of RM before and after sodium removal were analyzed using X-ray diffractometer (XRD) and scanning electron microscope (SEM), and the results showed that the alkaline materials in the red mud reacted with CO2 and the sodium content in solid phases decreased significantly after reaction. The sodium removal efficiency could reach up to 70% with scientific procedure. The results of this research will offer an efficient way for low-cost sodium removal.

Comparison of nitric oxide-induced oxidation of recombinant oxyhemoglobin subunits using a competition experiment.

PubMed

Lin, Yen-Lin; Huang, Kuang-Tse

2009-08-01

A low reaction rate with nitric oxide (NO) is one of the important characteristics of hemoglobin (Hb)-based oxygen carriers. The reaction rate between oxyHb and NO is usually measured by stopped-flow spectrophotometry. However, the reported rates vary due to the difficulty of accurately determining the NO concentration and the limit of the instrument dead time. To circumvent these problems, we developed an experiment using oxymyoglobin (oxyMb) to compete with oxyHb for NO that is released from an NO donor. Determination of the rate constants in the competition experiment no longer depends on accurate measurement of time or NO concentration, since this approach instead measures the ratio of rate constants for the reaction of oxyHb and oxyMb with NO. For recombinant mutant Hb alpha(L29F)beta the rates for alpha(L29F) and beta are approximately 15- and 1.6-fold smaller than for wild-type Hb. In conclusion, the competition experiment provides an alternative method for determination of relative reaction rates of recombinant Hb subunits with NO.

Entrapped Single Tungstate Site in Zeolite for Cooperative Catalysis of Olefin Metathesis with Brønsted Acid Site

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

Zhao, Pu; Ye, Lin; Sun, Zhenyu

Industrial olefin metathesis catalysts generally suffer from low reaction rates and require harsh reaction conditions for moderate activities. This is due to their inability to prevent metathesis active sites (MAS) from aggregation and their intrinsic poor adsorption and activation of olefin molecules. Here, isolated tungstate species as single molecular MAS is immobilized inside zeolite pores by Bronsted acid sites (BAS) on the inner surface. It is demonstrated for the first time that unoccupied BAS in atomic proximity to MAS enhance olefin adsorption and greatly facilitate the formation of metallocycle intermediates in a stereospecific manner. Thus, effective cooperative catalysis takes placemore » over the BAS-MAS pair. In consequence, for the cross-metathesis of ethene and trans-2-butene to propene, under the same mild reaction conditions, the propene production rate over WOx/USY is ca. 7,300 times that over the industrial WO3/SiO2 based catalyst. A propene yield up to 79% (80% selectivity) without observable deactivation was obtained over WOx/USY for a wide range of reaction conditions.« less

Density-dependent liquid nitromethane decomposition: molecular dynamics simulations based on ReaxFF.

PubMed

Rom, Naomi; Zybin, Sergey V; van Duin, Adri C T; Goddard, William A; Zeiri, Yehuda; Katz, Gil; Kosloff, Ronnie

2011-09-15

The decomposition mechanism of hot liquid nitromethane at various compressions was studied using reactive force field (ReaxFF) molecular dynamics simulations. A competition between two different initial thermal decomposition schemes is observed, depending on compression. At low densities, unimolecular C-N bond cleavage is the dominant route, producing CH(3) and NO(2) fragments. As density and pressure rise approaching the Chapman-Jouget detonation conditions (∼30% compression, >2500 K) the dominant mechanism switches to the formation of the CH(3)NO fragment via H-transfer and/or N-O bond rupture. The change in the decomposition mechanism of hot liquid NM leads to a different kinetic and energetic behavior, as well as products distribution. The calculated density dependence of the enthalpy change correlates with the change in initial decomposition reaction mechanism. It can be used as a convenient and useful global parameter for the detection of reaction dynamics. Atomic averaged local diffusion coefficients are shown to be sensitive to the reactions dynamics, and can be used to distinguish between time periods where chemical reactions occur and diffusion-dominated, nonreactive time periods. © 2011 American Chemical Society

T85C polymorphisms of the dihydropyrimidine dehydrogenase gene detected in gastric cancer tissues by high-resolution melting curve analysis.

PubMed

Fang, Weijia; Xu, Nong; Jin, Dazhi; Chen, Yu; Chen, Xiaogang; Zheng, Yi; Shen, Hong; Yuan, Ying; Zheng, Shusen

2012-01-01

Dihydropyrimidine dehydrogenase is a key enzyme acting on the metabolic pathway of medications for gastric cancer. High-resolution melting curve technology, which was developed recently, can distinguish the wild-type dihydropyrimidine dehydrogenase gene from multiple polymorphisms by fluorescent quantitative polymerase chain reaction products in a direct and effective manner. T85C polymorphisms of dihydropyrimidine dehydrogenase in the peripheral blood of 112 Chinese gastric cancer patients were detected by real-time polymerase chain reaction combined with high-resolution melting curve technology. Primer design, along with the reaction system and conditions, was optimized based on the GenBank sequence. Seventy nine cases of wild-type (TT, [70.5%]), 29 cases of heterozygous (TC, [25.9%]), and 4 cases of homozygous mutant (CC, [3.6%]) were observed. The result was completely consistent with the results of the sequencing. Real-time polymerase chain reaction combined with high-resolution melting curve technology is a rapid, simple, reliable, direct-viewing, and convenient method for the detection and screening of polymorphisms.

Graphene-oxide-supported CuAl and CoAl layered double hydroxides as enhanced catalysts for carbon-carbon coupling via Ullmann reaction

NASA Astrophysics Data System (ADS)

Ahmed, Nesreen S.; Menzel, Robert; Wang, Yifan; Garcia-Gallastegui, Ainara; Bawaked, Salem M.; Obaid, Abdullah Y.; Basahel, Sulaiman N.; Mokhtar, Mohamed

2017-02-01

Two efficient catalyst based on CuAl and CoAl layered double hydroxides (LDHs) supported on graphene oxide (GO) for the carbon-carbon coupling (Classic Ullmann Homocoupling Reaction) are reported. The pure and hybrid materials were synthesised by direct precipitation of the LDH nanoparticles onto GO, followed by a chemical, structural and physical characterisation by electron microscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), surface area measurements and X-ray photoelectron spectroscopy (XPS). The GO-supported and unsupported CuAl-LDH and CoAl-LDH hybrids were tested over the Classic Ullman Homocoupling Reaction of iodobenzene. In the current study CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%, respectively) at very short reaction times (25 min). GO provides a light-weight, charge complementary and two-dimensional material that interacts effectively with the 2D LDHs, in turn enhancing the stability of LDH. After 5 re-use cycles, the catalytic activity of the LDH/GO hybrid is up to 2 times higher than for the unsupported LDH.

Acceleration and sensitivity analysis of lattice kinetic Monte Carlo simulations using parallel processing and rate constant rescaling

NASA Astrophysics Data System (ADS)

Núñez, M.; Robie, T.; Vlachos, D. G.

2017-10-01

Kinetic Monte Carlo (KMC) simulation provides insights into catalytic reactions unobtainable with either experiments or mean-field microkinetic models. Sensitivity analysis of KMC models assesses the robustness of the predictions to parametric perturbations and identifies rate determining steps in a chemical reaction network. Stiffness in the chemical reaction network, a ubiquitous feature, demands lengthy run times for KMC models and renders efficient sensitivity analysis based on the likelihood ratio method unusable. We address the challenge of efficiently conducting KMC simulations and performing accurate sensitivity analysis in systems with unknown time scales by employing two acceleration techniques: rate constant rescaling and parallel processing. We develop statistical criteria that ensure sufficient sampling of non-equilibrium steady state conditions. Our approach provides the twofold benefit of accelerating the simulation itself and enabling likelihood ratio sensitivity analysis, which provides further speedup relative to finite difference sensitivity analysis. As a result, the likelihood ratio method can be applied to real chemistry. We apply our methodology to the water-gas shift reaction on Pt(111).

Theoretical and experimental studies on silica-coated carbon spheres composites

NASA Astrophysics Data System (ADS)

Guo, Xingmei; Liu, Haixing; Shen, Yinghua; Niu, Mei; Yang, Yongzhen; Liu, Xuguang

2013-10-01

In order to prepare carbon-based photonic crystals, first of all, theoretical modeling calculation was used to predict the bandgap characteristics of silica-coated carbon spheres. Then, silica-coated carbon spheres composites were synthesized using tetraethyl orthosilicate as precursor of silica by a sol-gel method combined with Stöber method. Effect of reaction conditions on surface coating of carbon spheres with silica, including the pH, the amount of precursor and reaction time, was emphasized. The morphology and structure of the composites and the effect coating of carbon spheres with silica were characterized by field-emission scanning electron microscopy, high resolution transmission electron microscopy and Fourier-transform infrared spectrometry. The coating ratio of silica was investigated by thermogravimetry. The results show that pH value played an important role in coating reaction, the dosage of the precursor and reaction time had significant effect on coating layer thickness, that is, coating ratio. Carbon spheres coated with silica had good dispersibility and dispersion stability in water and ethanol, which is preconditions of reactivity of carbon spheres in liquid phase and lays the basis for the application of carbon spheres.

Relationship Between Ebola Virus Real-Time Quantitative Polymerase Chain Reaction-Based Threshold Cycle Value and Virus Isolation From Human Plasma.

PubMed

Spengler, Jessica R; McElroy, Anita K; Harmon, Jessica R; Ströher, Ute; Nichol, Stuart T; Spiropoulou, Christina F

2015-10-01

We performed a longitudinal analysis of plasma samples obtained from 4 patients with Ebola virus (EBOV) disease (EVD) to determine the relationship between the real-time quantitative reverse transcriptase polymerase chain reaction (qRT-PCR)-based threshold cycle (Ct) value and the presence of infectious EBOV. EBOV was not isolated from plasma samples with a Ct value of >35.5 or >12 days after onset of symptoms. EBOV was not isolated from plasma samples in which anti-EBOV nucleoprotein immunoglobulin G was detected. These data demonstrate the utility of interpreting qRT-PCR results in the context of the course of EBOV infection and associated serological responses for patient-management decisions. Published by Oxford University Press on behalf of the Infectious Diseases Society of America 2015. This work is written by (a) US Government employee(s) and is in the public domain in the US.

A new method for solving the quantum hydrodynamic equations of motion: application to two-dimensional reactive scattering.

PubMed

Pauler, Denise K; Kendrick, Brian K

2004-01-08

The de Broglie-Bohm hydrodynamic equations of motion are solved using a meshless method based on a moving least squares approach and an arbitrary Lagrangian-Eulerian frame of reference. A regridding algorithm adds and deletes computational points as needed in order to maintain a uniform interparticle spacing, and unitary time evolution is obtained by propagating the wave packet using averaged fields. The numerical instabilities associated with the formation of nodes in the reflected portion of the wave packet are avoided by adding artificial viscosity to the equations of motion. The methodology is applied to a two-dimensional model collinear reaction with an activation barrier. Reaction probabilities are computed as a function of both time and energy, and are in excellent agreement with those based on the quantum trajectory method. (c) 2004 American Institute of Physics

A novel rapid genotyping technique for Collie eye anomaly: SYBR Green-based real-time polymerase chain reaction method applicable to blood and saliva specimens on Flinders Technology Associates filter paper.

PubMed

Chang, Hye-Sook; Mizukami, Keijiro; Yabuki, Akira; Hossain, Mohammad A; Rahman, Mohammad M; Uddin, Mohammad M; Arai, Toshiro; Yamato, Osamu

2010-09-01

Collie eye anomaly (CEA) is a canine inherited ocular disease that shows a wide variety of manifestations and severity of clinical lesions. Recently, a CEA-associated mutation was reported, and a DNA test that uses conventional polymerase chain reaction (PCR) has now become available. The objective of the current study was to develop a novel rapid genotyping technique by using SYBR Green-based real-time PCR for future large-scale surveys as a key part in the strategy to eradicate CEA by selective breeding. First, a SYBR Green-based real-time PCR assay for genotyping of CEA was developed and evaluated by using purified DNA samples from normal, carrier, and affected Border Collies in which genotypes had previously been determined by conventional PCR. This real-time PCR assay demonstrated appropriate amplifications in all genotypes, and the results were consistent with those of conventional PCR. Second, the availability of Flinders Technology Associates filter paper (FTA card) as DNA templates for the real-time PCR assay was evaluated by using blood and saliva specimens to determine suitability for CEA screening. DNA-containing solution prepared from a disc of blood- or saliva-spotted FTA cards was available directly as templates for the real-time PCR assay when the volume of solution was 2.5% of the PCR mixture. In conclusion, SYBR Green-based real-time PCR combined with FTA cards is a rapid genotyping technique for CEA that can markedly shorten the overall time required for genotyping as well as simplify the sample preparation. Therefore, this newly developed technique suits large-scale screening in breeding populations of Collie-related breeds.

Toward a microfluidic-based rapid amylase assay system.

PubMed

Holmes, Richard J; Summersgil, Philip; Ryan, Timothy; Brown, Bernard J Treves; Mockbil, Amal; Grieve, Bruce D; Fielden, Peter R

2009-08-01

This article describes work into a prototype system for the assay of amylase, using microfludic technologies. The new system has a significantly shorter cycle time than the current laboratory methods, which generally use microtitre plates, yet is capable of generating significantly superior results. As such, we have shown that sensitivity is enhanced by a factor of 10 in the standard assay trials, and by a factor of 2 in the real-sample lab trials. In both assays, the use of a microreactor system reduced the reaction time by a factor of 6.2, from 20 min incubation to 3.2 min. Basing the conclusion on the Megazyme Cerealpha Standard Method, and using the Cerealpha units as a measure of assay efficiency, the typical response for the microfluidic assay was shown to be 1.0 x 10(-3) CU/mL (standard deviation [SD] 2.5 x 10(-4) CU/mL), compared to 2.56 x 10(-4) CU/mL (SD 5.94 x 10(-5) CU/mL) for the standard macroassay. It is believed that this improvement in the reaction schematics is due to the inherent advantages of microfluidic devices such as superior mixing, higher thermal efficiency, and enhanced reaction kinetics.

Modeling of photodegradation in solar cell modules of substrate and superstrate design made with ethylene-vinyl acetate as pottant material

NASA Technical Reports Server (NTRS)

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

1981-01-01

The rates of hydrogen abstraction by peroxy radicals were proven to be too slow for significant oxidation of the alkane substrate to be important. The numerical procedure, independent of our particular data base was verified by reproducing concentration time profiles for a model reaction set describing the cesium flare system in the upper atmosphere. Simulation was identical to that given in the literature. Experimental verification of the data base is to be attempted by weatherometry studies in the coming year. Work on the new diagnostic techniques was completed. The adapted automated viscometer was demonstrated to be an efficient and reliable tool for routine measurements of viscosity (molecular weight) changes in solid samples after batch solutions have been made up. The laser photolysis GC method for monitoring extremely low levels of oxidation in polymers proved to be impractical because the yields of carbon monoxide were too low for quantification. Much progress was made with the computer model. The reaction matrix was completely revised, resulting in a new scheme of 31 reactions and time, lifetimes in excess of ten years. The results to date lead us to some tentative observations.

Adaptive extended-state observer-based fault tolerant attitude control for spacecraft with reaction wheels

NASA Astrophysics Data System (ADS)

Ran, Dechao; Chen, Xiaoqian; de Ruiter, Anton; Xiao, Bing

2018-04-01

This study presents an adaptive second-order sliding control scheme to solve the attitude fault tolerant control problem of spacecraft subject to system uncertainties, external disturbances and reaction wheel faults. A novel fast terminal sliding mode is preliminarily designed to guarantee that finite-time convergence of the attitude errors can be achieved globally. Based on this novel sliding mode, an adaptive second-order observer is then designed to reconstruct the system uncertainties and the actuator faults. One feature of the proposed observer is that the design of the observer does not necessitate any priori information of the upper bounds of the system uncertainties and the actuator faults. In view of the reconstructed information supplied by the designed observer, a second-order sliding mode controller is developed to accomplish attitude maneuvers with great robustness and precise tracking accuracy. Theoretical stability analysis proves that the designed fault tolerant control scheme can achieve finite-time stability of the closed-loop system, even in the presence of reaction wheel faults and system uncertainties. Numerical simulations are also presented to demonstrate the effectiveness and superiority of the proposed control scheme over existing methodologies.

Transient-state kinetic approach to mechanisms of enzymatic catalysis.

PubMed

Fisher, Harvey F

2005-03-01

Transient-state kinetics by its inherent nature can potentially provide more directly observed detailed resolution of discrete events in the mechanistic time courses of enzyme-catalyzed reactions than its more widely used steady-state counterpart. The use of the transient-state approach, however, has been severely limited by the lack of any theoretically sound and applicable basis of interpreting the virtual cornucopia of time and signal-dependent phenomena that it provides. This Account describes the basic kinetic behavior of the transient state, critically examines some currently used analytic methods, discusses the application of a new and more soundly based "resolved component transient-state time-course method" to the L-glutamate-dehydrogenase reaction, and establishes new approaches for the analysis of both single- and multiple-step substituted transient-state kinetic isotope effects.

Econophysics — complex correlations and trend switchings in financial time series

NASA Astrophysics Data System (ADS)

Preis, T.

2011-03-01

This article focuses on the analysis of financial time series and their correlations. A method is used for quantifying pattern based correlations of a time series. With this methodology, evidence is found that typical behavioral patterns of financial market participants manifest over short time scales, i.e., that reactions to given price patterns are not entirely random, but that similar price patterns also cause similar reactions. Based on the investigation of the complex correlations in financial time series, the question arises, which properties change when switching from a positive trend to a negative trend. An empirical quantification by rescaling provides the result that new price extrema coincide with a significant increase in transaction volume and a significant decrease in the length of corresponding time intervals between transactions. These findings are independent of the time scale over 9 orders of magnitude, and they exhibit characteristics which one can also find in other complex systems in nature (and in physical systems in particular). These properties are independent of the markets analyzed. Trends that exist only for a few seconds show the same characteristics as trends on time scales of several months. Thus, it is possible to study financial bubbles and their collapses in more detail, because trend switching processes occur with higher frequency on small time scales. In addition, a Monte Carlo based simulation of financial markets is analyzed and extended in order to reproduce empirical features and to gain insight into their causes. These causes include both financial market microstructure and the risk aversion of market participants.

Time-resolved gas-phase kinetic, quantum chemical, and RRKM studies of reactions of silylene with alcohols.

PubMed

Becerra, Rosa; Cannady, J Pat; Walsh, Robin

2011-05-05

Time-resolved kinetic studies of silylene, SiH(2), generated by laser flash photolysis of 1-silacyclopent-3-ene and phenylsilane, have been carried out to obtain rate constants for its bimolecular reactions with methanol, ethanol, 1-propanol, 1-butanol, and 2-methyl-1-butanol. The reactions were studied in the gas phase over the pressure range 1-100 Torr in SF(6) bath gas, at room temperature. In the study with methanol several buffer gases were used. All five reactions showed pressure dependences characteristic of third body assisted association reactions. The rate constant pressure dependences were modeled using RRKM theory, based on E(0) values of the association complexes obtained by ab initio calculation (G3 level). Transition state models were adjusted to fit experimental fall-off curves and extrapolated to obtain k(∞) values in the range (1.9-4.5) × 10(-10) cm(3) molecule(-1) s(-1). These numbers, corresponding to the true bimolecular rate constants, indicate efficiencies of between 16% and 67% of the collision rates for these reactions. In the reaction of SiH(2) + MeOH there is a small kinetic component to the rate which is second order in MeOH (at low total pressures). This suggests an additional catalyzed reaction pathway, which is supported by the ab initio calculations. These calculations have been used to define specific MeOH-for-H(2)O substitution effects on this catalytic pathway. Where possible our experimental and theoretical results are compared with those of previous studies.

GPU accelerated real-time confocal fluorescence lifetime imaging microscopy (FLIM) based on the analog mean-delay (AMD) method

PubMed Central

Kim, Byungyeon; Park, Byungjun; Lee, Seungrag; Won, Youngjae

2016-01-01

We demonstrated GPU accelerated real-time confocal fluorescence lifetime imaging microscopy (FLIM) based on the analog mean-delay (AMD) method. Our algorithm was verified for various fluorescence lifetimes and photon numbers. The GPU processing time was faster than the physical scanning time for images up to 800 × 800, and more than 149 times faster than a single core CPU. The frame rate of our system was demonstrated to be 13 fps for a 200 × 200 pixel image when observing maize vascular tissue. This system can be utilized for observing dynamic biological reactions, medical diagnosis, and real-time industrial inspection. PMID:28018724

Viewing Human DNA Polymerase β Faithfully and Unfaithfully Bypass an Oxidative Lesion by Time-Dependent Crystallography

DOE PAGES

Vyas, Rajan; Reed, Andrew J.; Tokarsky, E. John; ...

2015-03-31

One common oxidative DNA lesion, 8-oxo-7,8-dihydro-2'-deoxyguanine (8-oxoG), is highly mutagenic in vivo due to its anti-conformation forming a Watson–Crick base pair with correct deoxycytidine 5'-triphosphate (dCTP) and its syn-conformation forming a Hoogsteen base pair with incorrect deoxyadenosine 5'-triphosphate (dATP). Here in this article, we utilized time-resolved X-ray crystallography to follow 8-oxoG bypass by human DNA polymerase β (hPolβ). In the 12 solved structures, both Watson–Crick (anti-8-oxoG:anti-dCTP) and Hoogsteen (syn-8-oxoG:anti-dATP) base pairing were clearly visible and were maintained throughout the chemical reaction. Additionally, a third Mg 2+ appeared during the process of phosphodiester bond formation and was located between the reactingmore » α- and β-phosphates of the dNTP, suggesting its role in stabilizing reaction intermediates. After phosphodiester bond formation, hPolβ reopened its conformation, pyrophosphate was released, and the newly incorporated primer 3'-terminal nucleotide stacked, rather than base paired, with 8-oxoG. These structures provide the first real-time pictures, to our knowledge, of how a polymerase correctly and incorrectly bypasses a DNA lesion.« less

Viewing Human DNA Polymerase β Faithfully and Unfaithfully Bypass an Oxidative Lesion by Time-Dependent Crystallography

PubMed Central

Vyas, Rajan; Reed, Andrew J.; Tokarsky, E. John; Suo, Zucai

2015-01-01

One common oxidative DNA lesion, 8-oxo-7,8-dihydro-2′-deoxyguanine (8-oxoG), is highly mutagenic in vivo due to its anti-conformation forming a Watson–Crick base pair with correct deoxycytidine 5′-triphosphate (dCTP) and its syn-conformation forming a Hoogsteen base pair with incorrect deoxyadenosine 5′-triphosphate (dATP). Here, we utilized time-resolved X-ray crystallography to follow 8-oxoG bypass by human DNA polymerase β (hPolβ). In the 12 solved structures, both Watson–Crick (anti-8-oxoG:anti-dCTP) and Hoogsteen (syn-8-oxoG:anti-dATP) base pairing were clearly visible and were maintained throughout the chemical reaction. Additionally, a third Mg2+ appeared during the process of phosphodiester bond formation and was located between the reacting α- and β-phosphates of the dNTP, suggesting its role in stabilizing reaction intermediates. After phosphodiester bond formation, hPolβ reopened its conformation, pyrophosphate was released, and the newly incorporated primer 3′-terminal nucleotide stacked, rather than base paired, with 8-oxoG. These structures provide the first real-time pictures, to our knowledge, of how a polymerase correctly and incorrectly bypasses a DNA lesion. PMID:25825995

Biodegradable polyester-based eco-composites containing hemp fibers modified with macrocyclic oligomers

NASA Astrophysics Data System (ADS)

Conzatti, Lucia; Utzeri, Roberto; Hodge, Philip; Stagnaro, Paola

2016-05-01

An original compatibilizing pathway for hemp fibers/poly(1,4-butylene adipate-co-terephtalate) (PBAT) eco-composites was explored exploiting the capability of macrocyclic oligomers (MCOs), obtained by cyclodepolymerization (CDP) of PBAT at high dilution, of being re-converted into linear chains by entropically-driven ring-opening polymerization (ED-ROP) that occurs simply heating the MCOS in the bulk. CDP reaction of PBAT was carried out varying solvent, catalyst and reaction time. Selected MCOs were used to adjust the conditions of the ED-ROP reaction. The best experimental conditions were then adopted to modify hemp fibers. Eco-composites based on PBAT and hemp fibers as obtained or modified with PBAT macrocyclics or oligomers were prepared by different process strategies. The best fiber-PBAT compatibility was observed when the fibers were modified with PBAT oligomers before incorporation in the polyester matrix.

Neutrino-induced meson productions off nucleon at forward limit in nucleon resonance region

NASA Astrophysics Data System (ADS)

Nakamura, S. X.; Kamano, H.; Lee, T.-S. H.; Sato, T.

2015-05-01

We study forward neutrino-induced meson production off the nucleon in the resonance region. Our calculation is based on a dynamical coupled-channels (DCC) model that reasonably describes π(γ)N → πN, ηN, KΛ, KΣ data in the resonance region. We apply the PCAC hypothesis to the DCC model to relate the πN reaction amplitude to the forward neutrino reaction amplitude. In this way, we give a prediction for νN → πN, ππN, ηN, KΛ, KΣ reaction cross sections. The predicted νN → ππN, ηN, KΛ, KΣ cross sections are, for the first time, based on a model extensively tested by data. We compare our results with those from the Rein-Sehgal model that has been very often used in the existing Monte Carlo simulators for neutrino experiments. We find a significant difference between them.

Pulse-density modulation control of chemical oscillation far from equilibrium in a droplet open-reactor system

PubMed Central

Sugiura, Haruka; Ito, Manami; Okuaki, Tomoya; Mori, Yoshihito; Kitahata, Hiroyuki; Takinoue, Masahiro

2016-01-01

The design, construction and control of artificial self-organized systems modelled on dynamical behaviours of living systems are important issues in biologically inspired engineering. Such systems are usually based on complex reaction dynamics far from equilibrium; therefore, the control of non-equilibrium conditions is required. Here we report a droplet open-reactor system, based on droplet fusion and fission, that achieves dynamical control over chemical fluxes into/out of the reactor for chemical reactions far from equilibrium. We mathematically reveal that the control mechanism is formulated as pulse-density modulation control of the fusion–fission timing. We produce the droplet open-reactor system using microfluidic technologies and then perform external control and autonomous feedback control over autocatalytic chemical oscillation reactions far from equilibrium. We believe that this system will be valuable for the dynamical control over self-organized phenomena far from equilibrium in chemical and biomedical studies. PMID:26786848

Pulse-density modulation control of chemical oscillation far from equilibrium in a droplet open-reactor system.

PubMed

Sugiura, Haruka; Ito, Manami; Okuaki, Tomoya; Mori, Yoshihito; Kitahata, Hiroyuki; Takinoue, Masahiro

2016-01-20

The design, construction and control of artificial self-organized systems modelled on dynamical behaviours of living systems are important issues in biologically inspired engineering. Such systems are usually based on complex reaction dynamics far from equilibrium; therefore, the control of non-equilibrium conditions is required. Here we report a droplet open-reactor system, based on droplet fusion and fission, that achieves dynamical control over chemical fluxes into/out of the reactor for chemical reactions far from equilibrium. We mathematically reveal that the control mechanism is formulated as pulse-density modulation control of the fusion-fission timing. We produce the droplet open-reactor system using microfluidic technologies and then perform external control and autonomous feedback control over autocatalytic chemical oscillation reactions far from equilibrium. We believe that this system will be valuable for the dynamical control over self-organized phenomena far from equilibrium in chemical and biomedical studies.

Batch and Flow Photochemical Benzannulations Based on the Reaction of Ynamides and Diazo Ketones. Application to the Synthesis of Polycyclic Aromatic and Heteroaromatic Compounds

PubMed Central

Willumstad, Thomas P.; Haze, Olesya; Mak, Xiao Yin; Lam, Tin Yiu; Wang, Yu-Pu; Danheiser*, Rick L.

2013-01-01

Highly substituted polycyclic aromatic and heteroaromatic compounds are produced via a two-stage tandem benzannulation/cyclization strategy. The initial benzannulation step proceeds via a pericyclic cascade mechanism triggered by thermal or photochemical Wolff rearrangement of a diazo ketone. The photochemical process can be performed using a continuous flow reactor which facilitates carrying out reactions on a large scale and minimizes the time required for photolysis. Carbomethoxy ynamides as well as more ketenophilic bissilyl ynamines and N-sulfonyl and N-phosphoryl ynamides serve as the reaction partner in the benzannulation step. In the second stage of the strategy, RCM generates benzofused nitrogen heterocycles, and various heterocyclization processes furnish highly substituted and polycyclic indoles of types that were not available by using the previous cyclobutenone-based version of the tandem strategy. PMID:24116731

Microwave-Assisted Rapid Enzymatic Synthesis of Nucleic Acids.

PubMed

Hari Das, Rakha; Ahirwar, Rajesh; Kumar, Saroj; Nahar, Pradip

2016-07-02

Herein we report microwave-induced enhancement of the reactions catalyzed by Escherichia coli DNA polymerase I and avian myeloblastosis virus-reverse transcriptase. The reactions induced by microwaves result in a highly selective synthesis of nucleic acids in 10-50 seconds. In contrast, same reactions failed to give desired reaction products when carried out in the same time periods, but without microwave irradiation. Each of the reactions was carried out for different duration of microwave exposure time to find the optimum reaction time. The products produced by the respective enzyme upon microwave irradiation of the reaction mixtures were identical to that produced by the conventional procedures. As the microwave-assisted reactions are rapid, microwave could be a useful alternative to the conventional and time consuming procedures of enzymatic synthesis of nucleic acids.

Real-time PCR assays for detection and quactification of Edwardsiella tarda, Edwardsiella piscicida, Edwardsiella piscicida-like sp. in catfish tissues and pond water

USDA-ARS?s Scientific Manuscript database

Researchers have proposed the adoption of 3 distinct genetic taxa among bacteria previously classified as Edwardsiella tarda; namely E. tarda, E. piscicida, and a taxon presently termed E. piscicida–like. Individual real-time polymerase chain reaction (qPCR) assays were developed, based on published...

Development of a non invasion real-time PCR assay for the quantitation of chicken parvovirus in fecal swabs

USDA-ARS?s Scientific Manuscript database

The present study describes the development of a real time Taqman polymerase chain reaction (PCR) assay using a fluorescent labeled probe for the detection and quantitation of chicken parvovirus (ChPV) in feces. The primers and probes were designed based on the nucleotide sequence of the non struct...

The Processing of Singular and Plural Nouns in French and English

ERIC Educational Resources Information Center

New, Boris; Brysbaert, Marc; Segui, Juan; Ferrand, Ludovic; Rastle, Kathleen

2004-01-01

Contradictory data have been obtained about the processing of singular and plural nouns in Dutch and English. Whereas the Dutch findings point to an influence of the base frequency of the singular and the plural word forms on lexical decision times (Baayen, Dijkstra, & Schreuder, 1997), the English reaction times depend on the surface frequency of…

Optimization of random PEGylation reactions by means of high throughput screening.

PubMed

Maiser, Benjamin; Dismer, Florian; Hubbuch, Jürgen

2014-01-01

Since the first FDA approval of a PEGylated product in 1990, so called random PEGylation reactions are still used to increase the efficacy of biopharmaceuticals and represent the major technology of all approved PEG-modified drugs. However, the great influence of process parameters on PEGylation degree and the PEG-binding site results in a lack of reaction specificity which can have severe impact on the product profile. Consequently, reproducible and well characterized processes are essential to meet increasing regulative requirements resulting from the quality-by-design (QbD) initiative, especially for this kind of modification type. In this study we present a general approach which combines the simple chemistry of random PEGylation reactions with high throughput experimentation (HTE) to achieve a well-defined process. Robotic based batch experiments have been established in a 96-well plate format and were analyzed to investigate the influence of different PEGylation conditions for lysozyme as model protein. With common SEC analytics highly reproducible reaction kinetics were measured and a significant influence of PEG-excess, buffer pH, and reaction time could be investigated. Additional mono-PEG-lysozyme analytics showed the impact of varying buffer pH on the isoform distribution, which allowed us to identify optimal process parameters to get a maximum concentration of each isoform. Employing Micrococcus lysodeikticus based activity assays, PEG-lysozyme33 was identified to be the isoform with the highest residual activity, followed by PEG-lysozyme1 . Based on these results, a control space for a PEGylation reaction was defined with respect to an optimal overall volumetric activity of mono-PEG-lysozyme isoform mixtures. © 2013 Wiley Periodicals, Inc.

[Determination of serum acetaminophen based on the diazo reaction and its application in the evaluation of gastric emptying].

PubMed

Li, Cai-na; Sun, Su-juan; Shen, Zhu-fang

2015-05-01

This study aims to establish a method to determine the serum acetaminophen concentration based on diazo reaction, and apply it in the gastric emptying evaluation. Theoretically, acetaminophen could take hydrolysis reaction in hydrochloric acid solution to produce p-aminophenol, which could then take diazo reaction resulting in a product with special absorption peak at 312 nm. Then the serum acetaminophen concentration and recovery rate were calculated according to the standard curve drawn with absorbance at 312 nm. ICR mice were given a dose of acetaminophen (500 mg x kg(-1)) by gavage and the serum acetaminophen was dynamically measured through the diazo reaction. Besides, ICR mice were subcutaneously injected with the long-acting GLP-1 analog GW002 before the gavage of acetaminophen, and serum acetaminophen concentration was measured as above to study how GW002 could influence the gastric emptying. The data showed acetaminophen ranging from 0 to 160 μg x mL(-1) could take diazo reaction with excellent linear relationship, and the regression equation was y = 0.0181 x +0.0104, R2 = 0.9997. The serum acetaminophen was also measured with good linear relationship (y = 0.0045 x + 0.0462, R = 0.9982) and the recovery rate was 97.4%-116.7%. The serum concentration of acetaminophen reached peak at about 0.5 h after gavage, and then gradually decreased. GW002 could significantly lower the serum acetaminophen concentration and make the area under the concentration-time curve (AUC) decrease by 28.4%. In conclusion, a method for the determination of serum acetaminophen based on the diazo reaction was established with good accuracy and could be used in the evaluation of gastric emptying.