Reactions of animals and people under conditions of brief weightlessness

NASA Technical Reports Server (NTRS)

Kitayev-Smik, L. A.

1975-01-01

It has been shown that under brief weightlessness sensory reactions arise in a number of people, mainly those under these conditions for the first time, in the form of spatial and visual illusions, motor excitation, in which tonic and motor components can be distinguished, and vestibular-vegetative disturbances (nausea, vomiting, etc.). In repeated flights with creation of weightlessness, a decrease in the extent of expression and, then, disappearance of these reactions occurred in a significant majority of those studied. Experiments in weightlessness with the vision cut off and with the absence of vestibular functions in the subjects confirm the hypothesis that spatial conceptions of people in weightlessness depend on predominance of gravireceptor or visual afferent signals under these conditions.

Achieving Chemical Equilibrium: The Role of Imposed Conditions in the Ammonia Formation Reaction

ERIC Educational Resources Information Center

Tellinghuisen, Joel

2006-01-01

Under conditions of constant temperature T and pressure P, chemical equilibrium occurs in a closed system (fixed mass) when the Gibbs free energy G of the reaction mixture is minimized. However, when chemical reactions occur under other conditions, other thermodynamic functions are minimized or maximized. For processes at constant T and volume V,…

Reversible Hydrolysis Reaction with the Spore Photoproduct under Alkaline Conditions.

PubMed

Adhikari, Surya; Lin, Gengjie; Li, Lei

2016-09-16

DNA lesions may reduce the electron density at the nucleobases, making them prone to further modifications upon the alkaline treatment. The dominant DNA photolesion found in UV-irradiated bacterial endospores is a thymine dimer, 5-thyminyl-5,6-dihydrothymine, i.e., the spore photoproduct (SP). Here we report a stepwise addition/elimination reaction in the SP hydrolysis product under strong basic conditions where a ureido group is added to the carboxyl moiety to form a cyclic amide, regenerating SP after eliminating a hydroxide ion. Direct amidation of carboxylic acids by reaction with amines in the presence of a catalyst is well documented; however, it is very rare for an amidation reaction to occur without activation. This uncatalyzed SP reverse reaction in aqueous solution is even more surprising because the carboxyl moiety is not a good electrophile due to the negative charge it carries. Examination of the base-catalyzed hydrolyses of two other saturated pyrimidine lesions, 5,6-dihydro-2'-deoxyuridine and pyrimidine (6-4) pyrimidone photoproduct, reveals that neither reaction is reversible even though all three hydrolysis reactions may share the same gem-diol intermediate. Therefore, the SP structure where the two thymine residues maintain a stacked conformation likely provides the needed framework enabling this highly unusual carboxyl addition/elimination reaction.

Synchronization of Reaction-Diffusion Neural Networks With Dirichlet Boundary Conditions and Infinite Delays.

PubMed

Sheng, Yin; Zhang, Hao; Zeng, Zhigang

2017-10-01

This paper is concerned with synchronization for a class of reaction-diffusion neural networks with Dirichlet boundary conditions and infinite discrete time-varying delays. By utilizing theories of partial differential equations, Green's formula, inequality techniques, and the concept of comparison, algebraic criteria are presented to guarantee master-slave synchronization of the underlying reaction-diffusion neural networks via a designed controller. Additionally, sufficient conditions on exponential synchronization of reaction-diffusion neural networks with finite time-varying delays are established. The proposed criteria herein enhance and generalize some published ones. Three numerical examples are presented to substantiate the validity and merits of the obtained theoretical results.

Biogeochemical Reactions Under Simulated Europa Ocean Conditions

NASA Astrophysics Data System (ADS)

Amashukeli, X.; Connon, S. A.; Gleeson, D. F.; Kowalczyk, R. S.; Pappalardo, R. T.

2007-12-01

Galileo data have demonstrated the probable presence of a liquid water ocean on Europa, and existence of salts and carbon dioxide in the satellite's surface ice (e.g., Carr et al., 1998; McCord et al., 1999, Pappalardo et al., 1999; Kivelson et al., 2000). Subsequently, the discovery of chemical signatures of extinct or extant life in Europa's ocean and on its surface became a distinct possibility. Moreover, understanding of Europa's potential habitability is now one of the major goals of the Europa Orbiter Flagship mission. It is likely, that in the early stages of Europa's ocean formation, moderately alkaline oceanic sulfate-carbonate species and a magnetite-silicate mantel could have participated in low-temperature biogeochemical sulfur, iron and carbon cycles facilitated by primitive organisms (Zolotov and Shock, 2004). If periodic supplies of fresh rock and sulfate-carbonate ions are available in Europa's ocean, then an exciting prospect exists that life may be present in Europa's ocean today. In our laboratory, we began the study of the plausible biogeochemical reactions under conditions appropriate to Europa's ocean using barophilic psychrophilic organisms that thrive under anaerobic conditions. In the near absence of abiotic synthetic pathways due to low Europa's temperatures, the biotic synthesis may present a viable opportunity for the formation of the organic and inorganic compounds under these extreme conditions. This work is independent of assumptions regarding hydrothermal vents at Europa's ocean floor or surface-derived oxidant sources. For our studies, we have fabricated a high-pressure (5,000 psi) reaction vessel that simulates aqueous conditions on Europa. We were also successful at reviving barophilic psychrophilic strains of Shewanella bacterium, which serve as test organisms in this investigation. Currently, facultative barophilic psychrophilic stains of Shewanella are grown in the presence of ferric food source; the strains exhibiting iron

Experimental Studies of Hydrogenation and Other Reactions on Surfaces Under Astrophysically Relevant Conditions

NASA Technical Reports Server (NTRS)

Vidali, Gianfranco

1998-01-01

The goal of our project is to study hydrogen recombination reactions on solid surfaces under conditions that are relevant in astrophysics. Laboratory experiments were conducted using low-flux, cold atomic H and D beams impinging on a sample kept under ultra high vacuum conditions. Realistic analogues of interstellar dust grains were used. Our results show that current models for hydrogen recombination reactions have to be modified to take into account the role of activated diffusion of H on surfaces even at low temperature.

Onset conditions for gas phase reaction and nucleation in the CVD of transition metal oxides

NASA Technical Reports Server (NTRS)

Collins, J.; Rosner, D. E.; Castillo, J.

1992-01-01

A combined experimental/theoretical study is presented of the onset conditions for gas phase reaction and particle nucleation in hot substrate/cold gas CVD of transition metal oxides. Homogeneous reaction onset conditions are predicted using a simple high activation energy reacting gas film theory. Experimental tests of the basic theory are underway using an axisymmetric impinging jet CVD reactor. No vapor phase ignition has yet been observed in the TiCl4/O2 system under accessible operating conditions (below substrate temperature Tw = 1700 K). The goal of this research is to provide CVD reactor design and operation guidelines for achieving acceptable deposit microstructures at the maximum deposition rate while simultaneously avoiding homogeneous reaction/nucleation and diffusional limitations.

Effects of Meteorological Conditions on Reactions to Noise Exposure

NASA Technical Reports Server (NTRS)

Shepherd, Kevin P. (Technical Monitor); Fields, James M.

2004-01-01

More than 80,000 residents' responses to transportation noise at different times of year provide the best, but imprecise, statistical estimates of the effects of season and meteorological conditions on community response to noise. Annoyance with noise is found to be slightly statistically significantly higher in the summer than in the winter in a seven-year study in the Netherlands. Analyses of 41 other surveys drawn from diverse countries, climates, and times of year find noise annoyance is increased by temperature, and may be increased by more sunshine, less precipitation, and reduced wind speeds. Meteorological conditions on the day of the interview or the immediately preceding days do not appear to have any more effect on reactions than do the conditions over the immediately preceding weeks or months.

Future Challenges in Heterogeneous Catalysis: Understanding Catalysts under Dynamic Reaction Conditions

PubMed Central

Kalz, Kai F.; Kraehnert, Ralph; Dvoyashkin, Muslim; Dittmeyer, Roland; Gläser, Roger; Krewer, Ulrike; Reuter, Karsten

2016-01-01

Abstract In the future, (electro‐)chemical catalysts will have to be more tolerant towards a varying supply of energy and raw materials. This is mainly due to the fluctuating nature of renewable energies. For example, power‐to‐chemical processes require a shift from steady‐state operation towards operation under dynamic reaction conditions. This brings along a number of demands for the design of both catalysts and reactors, because it is well‐known that the structure of catalysts is very dynamic. However, in‐depth studies of catalysts and catalytic reactors under such transient conditions have only started recently. This requires studies and advances in the fields of 1) operando spectroscopy including time‐resolved methods, 2) theory with predictive quality, 3) kinetic modelling, 4) design of catalysts by appropriate preparation concepts, and 5) novel/modular reactor designs. An intensive exchange between these scientific disciplines will enable a substantial gain of fundamental knowledge which is urgently required. This concept article highlights recent developments, challenges, and future directions for understanding catalysts under dynamic reaction conditions. PMID:28239429

Using Group-Inquiry to Study Differing Reaction Conditions in the E2 Elimination of Cyclohexyl Halides

ERIC Educational Resources Information Center

Long, Robert D.

2012-01-01

In this experiment, students individually conduct one of several variations of an E2 dehydrohalogenation reaction on a cyclohexyl halide substrate for 30 min, which is sufficient only for a partial reaction to occur. The variations examine reaction conditions including different leaving groups, decreased reaction temperature, or reduced base…

The influence of reaction conditions on the Diels-Alder cycloadditions of 2-thio-3-chloroacrylamides; investigation of thermal, catalytic and microwave conditions.

PubMed

Kissane, Marie; Lynch, Denis; Chopra, Jay; Lawrence, Simon E; Maguire, Anita R

2010-12-21

The Diels-Alder cycloadditions of cyclopentadiene and 2,3-dimethyl-1,3-butadiene to a range of 2-thio-3-chloroacrylamides under thermal, catalytic and microwave conditions is described. The influence of reaction conditions on the outcome of the cycloadditions, in particular the stereoselectivity and reaction efficiency, is discussed. While the cycloadditions have been attempted at the sulfide, sulfoxide and sulfone levels of oxidation, use of the sulfoxide derivatives is clearly beneficial for stereoselective construction of Diels-Alder cycloadducts.

Influence of Exposure Conditions on the Efficacy of Lithium Nitrate in Mitigating Alkali Silica Reaction

NASA Astrophysics Data System (ADS)

Zapała-Sławeta, Justyna; Owsiak, Zdzisława

2017-10-01

Lithium nitrate is known to have the highest potential to inhibit alkali silica reaction in concrete. It is well soluble in water and does not increase the pH of concrete pore solution. The extent to which the alkali silica reaction is mitigated is affected by the amount of the applied lithium ions, exposure conditions and by the kind of reactive aggregate. It is known that some lithium compounds such as lithium carbonate or lithium fluoride, when used in insufficient amount, may increase expansion due to alkali silica reaction. This effect was not detected in the presence of lithium nitrate. The aim of this study was to determine the effect of lithium nitrate on alkali silica reaction in mortars exposed to different conditions. Expansion studies were conducted in accordance with the accelerated mortar bar test (ASTM C1260) and the standard mortar bar test (ASTM C227). It was observed that the long-term expansion results are different from the values obtained in the accelerated mortar bar test. Lithium nitrate does not reduce ASR-induced expansion when mortars are stored under conditions specified in ASTM C 227. The microstructure of the mortar samples exposed to different conditions was examined and X-ray microanalysis was performed. The microstructure and compositions of the alkali-silica reaction products varied. The amount of alkali silica gel in mortars with lithium nitrate in which the expansion was high was greater than that in the mortar bars tested by accelerated method.

The Emotional Stress Reaction Questionnaire (ESRQ): Measurement of Stress Reaction Level in Field Conditions in 60 Seconds

DTIC Science & Technology

2011-04-01

of coherence, secondary appraisal , cognitive emotion-focused coping , self-rated performance, self-rated health and a low moral stress reaction. The...1989). Personality, appraisal and cognitive coping processes, and performance during various conditions of stress . Military Psychology, 1, 167-182...Psychology, 2, 63-78. Larsson, G., Kempe, S., & Starrin, B. (1988). Appraisal and coping processes in acute, time-limited stressful situations: A

Reaction of N,N-Dimethyltryptamine with Dichloromethane Under Common Experimental Conditions.

PubMed

Dunlap, Lee E; Olson, David E

2018-05-31

A large number of clinically used drugs and experimental pharmaceuticals possess the N , N -dimethyltryptamine (DMT) structural core. Previous reports have described the reaction of this motif with dichloromethane (DCM), a common laboratory solvent used during extraction and purification, leading to the formation of an undesired quaternary ammonium salt byproduct. However, the kinetics of this reaction under various conditions have not been thoroughly described. Here, we report a series of experiments designed to simulate the exposure of DMT to DCM that would take place during extraction from plant material, biphasic aqueous work-up, or column chromatography purification. We find that the quaternary ammonium salt byproduct forms at an exceedingly slow rate, only accumulates to a significant extent upon prolonged exposure of DMT to DCM, and is readily extracted into water. Our results suggest that DMT can be exposed to DCM under conditions where contact times are limited (<30 min) with minimal risk of degradation and that this byproduct is not observed following aqueous extraction. However, alternative solvents should be considered when the experimental conditions require longer contact times. Our work has important implications for preparing a wide-range of pharmaceuticals bearing the DMT structural motif in high yields and purities.

Ablation characteristics and reaction mechanism of insulation materials under slag deposition condition

NASA Astrophysics Data System (ADS)

Guan, Yiwen; Li, Jiang; Liu, Yang

2017-07-01

Current understanding of the physical and chemical processes involved in the ablation of insulation materials by highly aluminized solid propellants is limited. The study on the heat transfer and ablation principle of ethylene propylene diene monomer (EPDM) materials under slag deposition condition is essential for future design or modification of large solid rocket motors (SRMs) for launch application. In this paper, the alumina liquid flow pattern and the deposition principle in full-scale SRM engines are discussed. The interaction mechanism between the alumina droplets and the wall are analyzed. Then, an experimental method was developed to simulate the insulation material ablation under slag deposition condition. Experimental study was conducted based on a laboratory-scale device. Meanwhile, from the analysis of the cross-sectional morphology and chemical composition of the charring layer after ablation, the reaction mechanism of the charring layer under deposition condition was discussed, and the main reaction equation was derived. The numerical simulation and experimental results show the following. (i) The alumina droplet flow in the deposition section of the laboratory-scale device is similar to that of a full-scale SRM. (ii) The charring layer of the EPDM insulator displays a porous tight/loose structure under high-temperature slag deposition condition. (iii) A seven-step carbothermal reduction in the alumina is derived and established under high-pressure and high-temperature environment in the SRM combustion chamber. (iv) The analysis using thermodynamic software indicates that the reaction of the alumina and charring layer initially forms Al4C3 during the operation. Then, Al element and Al2OC compound are subsequently produced with the reduction in the release of gas CO as well with continuous environmental heating.

The kinetics of dolomite reaction rim growth under isostatic and non-isostatic pressure conditions

NASA Astrophysics Data System (ADS)

Helpa, V.; Rybacki, E.; Morales, L. G.; Abart, R.; Dresen, G. H.

2013-12-01

During burial and exhumation, rocks are simultaneously exposed to metamorphic reactions and tectonic stresses. Therefore, the reaction rate of newly formed minerals may depend on chemical and mechanical driving forces. Here, we investigate the reaction kinetics of dolomite (CaMg[CO3]2) rim growth by solid-state reactions experiments on oriented calcite (CaCO3) and magnesite (MgCO3) single crystals under isostatic and non-isostatic pressure conditions. Cylindrical samples of 3-5 mm length and 7 mm diameter were drilled and polished perpendicular to the rhombohedral cleavage planes of natural clear crystals. The tests were performed using a Paterson-type deformation apparatus at P = 400 MPa confining pressure, temperatures, T, between 750 and 850°C, and reaction durations, t, of 2 - 146 h to calculate the kinetic parameters of dolomite rim growth under isostatic stress conditions. For non-isostatic reaction experiments we applied in addition differential stresses, σ, up to 40 MPa perpendicular to the contact interface at T = 750°C for 4 - 171 h duration, initiating minor inelastic deformation of calcite. The thickness of the resulting dolomite reaction rims increases linearly with the square root of time, indicating a diffusion-controlled reaction. The rims consist of two different textural domains. Granular dolomite grains (≈ 2 -5 μm grain size) form next to calcite and elongated palisade-shaped grains (1-6 μm diameter) grow perpendicular to the magnesite interface. Texture measurements with the electron backscatter diffraction technique indicate that the orientations of dolomite grains are mainly influenced by the orientation of the calcite educt crystal, in particular in the granular rim. To some extent, the texture of dolomite palisades is also influenced by the orientation of magnesite. The thickness of the two individual layers increases with temperature. At 400 MPa isostatic pressure, T = 750°C and t = 29 hours, a 5 μm thick granular dolomite layer

A comparison between taste avoidance and conditioned disgust reactions induced by ethanol and lithium chloride in preweanling rats.

PubMed

Arias, Carlos; Pautassi, Ricardo Marcos; Molina, Juan Carlos; Spear, Norman E

2010-09-01

Adult rats display taste avoidance and disgust reactions when stimulated with gustatory stimuli previously paired with aversive agents such as lithium chloride (LiCl). By the second postnatal week of life, preweanling rats also display specific behaviors in response to a tastant conditioned stimulus (CS) that predicts LiCl-induced malaise. The present study compared conditioned disgust reactions induced by LiCl or ethanol (EtOH) in preweanling rats. In Experiment 1 we determined doses of ethanol and LiCl that exert similar levels of conditioned taste avoidance. After having equated drug dosage in terms of conditioned taste avoidance, 13-day-old rats were given a single pairing of a novel taste (saccharin) and either LiCl or ethanol (2.5 g/kg; Experiment 2). Saccharin intake and emission of disgust reactions were assessed 24 and 48 hr after training. Pups given paired presentations of saccharin and the aversive agents (ethanol or LiCl) consumed less saccharin during the first testing day than controls. These pups also showed more aversive behavioral reactions to the gustatory CS than controls. Specifically, increased amounts of grooming, general activity, head shaking, and wall climbing as well as reduced mouthing were observed in response to the CS. Conditioned aversive reactions but not taste avoidance were still evident on the second testing day. In conclusion, a taste CS paired with postabsorptive effects of EtOH and LiCl elicited a similar pattern of conditioned rejection reactions in preweanling rats. These results suggest that similar mechanisms may be underlying CTAs induced by LiCl and a relatively high EtOH dose.

Runaway reactions, their courses and the methods to establish safe process conditions

NASA Astrophysics Data System (ADS)

Gustin, J. L.

1991-08-01

Much of the literature on runaway reactions deals with the consequences such as mechanical damage toxic and flammable release. The DIERS literature provides effective methods for vent sizing where experimental information is requested. Thermal stability measurements provide information on the onset temperature and kinetic data for chemical reactions. There is less information on the way the runaway reactions occur whereas the runaway reactions may have different causes. The purpose of this paper is to describe the various process deviations which can cause a runaway reaction to occur and to discuss the experimental information necessary for risk assessment, the choice of a safe process and the mitigation of the consequences of the runaway reaction. Each possible hazardous process deviation is illustrated by examples from the process industry and/or relevant experimental information obtained from laboratory experiments. The typical hazardous situations to be considered are the following: 1) The homogeneous thermal runaway due to too high a temperature. 2) The homogeneous runaway reaction by unintended introduction of additional reactants or catalyst. 3) The heterogeneous runaway reaction due to too high a local temperature. 4) The heterogeneous runaway reaction caused by slow heat conduction to the outside. 5) The runaway reaction caused by excess residence time at the process temperature (autocatalytic reactions). 6) The runaway reaction caused by reactant accumulation. The controling reactant feed rate is higher than the consumption rate perhaps because the temperature is too low, or the catalyst is absent. 7) The runaway reaction due to the pressurization of the enclosure by gaseous oxidizing intermediates (typical of nitric oxidations). 8) The runaway reaction due to phase separation of unstable species (liquids, solids) by loss of mixing or on cooling. 9) The runaway reaction on mixing of fast reacting chemicals in separate phases. 10)The runaway reaction due

Review and analysis of high temperature chemical reactions and the effect of non-equilibrium conditions

NASA Technical Reports Server (NTRS)

Johnson, R. E.

1986-01-01

Chemical reactions at high temperatures have been considered extensively because of their importance to the heating effects on re-entry of space vehicles. Data on these reactions however, are not abundant and even when found there are discrepancies in data collected by various investigators. In particular, data for recombination reactions are calculated from the dissociation reactions or vice versa through the equilibrium constant. This involves the use of the principle of detailed balancing. This principle is discussed in reference to conditions where it is valid as well as to those where it is not valid. Related topics that merit further study or for which applicable information was available are briefly mentioned in an appendix to this report.

Contaminant transport in soil with depth-dependent reaction coefficients and time-dependent boundary conditions.

PubMed

Gao, Guangyao; Fu, Bojie; Zhan, Hongbin; Ma, Ying

2013-05-01

Predicting the fate and movement of contaminant in soils and groundwater is essential to assess and reduce the risk of soil contamination and groundwater pollution. Reaction processes of contaminant often decreased monotonously with depth. Time-dependent input sources usually occurred at the inlet of natural or human-made system such as radioactive waste disposal site. This study presented a one-dimensional convection-dispersion equation (CDE) for contaminant transport in soils with depth-dependent reaction coefficients and time-dependent inlet boundary conditions, and derived its analytical solution. The adsorption coefficient and degradation rate were represented as sigmoidal functions of soil depth. Solute breakthrough curves (BTCs) and concentration profiles obtained from CDE with depth-dependent and constant reaction coefficients were compared, and a constant effective reaction coefficient, which was calculated by arithmetically averaging the depth-dependent reaction coefficient, was proposed to reflect the lumped depth-dependent reaction effect. With the effective adsorption coefficient and degradation rate, CDE could produce similar BTCs and concentration profiles as those from CDE with depth-dependent reactions in soils with moderate chemical heterogeneity. In contrast, the predicted concentrations of CDE with fitted reaction coefficients at a certain depth departed significantly from those of CDE with depth-dependent reactions. Parametric analysis was performed to illustrate the effects of sinusoidally and exponentially decaying input functions on solute BTCs. The BTCs and concentration profiles obtained from the solutions for finite and semi-infinite domain were compared to investigate the effects of effluent boundary condition. The finite solution produced higher concentrations at the increasing limb of the BTCs and possessed a higher peak concentration than the semi-infinite solution which had a slightly long tail. Furthermore, the finite solution gave

Correlation changes in EEG, conditioned and behavioral reactions with various degrees of oxygen insufficiency

NASA Technical Reports Server (NTRS)

Agadzhanyan, N. A.; Zakharova, I. N.; Kalyuzhnyy, L. V.; Dvorzhak, I. I.; Moravek, M.; Tsmiral, Y. I.

1974-01-01

The dynamics of change in bioelectric activity of the brain during acute hypoxia are studied for the time that working capacity and active consciousness are preserved, and to establish the correlation between EEG changes and behavioral reactions under oxygen starvation. Changes in body functions and behavioral disturbances are related to the degree of oxygen saturation in the blood, to bioelectric activity of the brain, and to an increase in conditioned reflexes. The capacity for adequate reaction to external signals and for coordinated psychomotor activity after loss of consciousness returns to man after 30 seconds. Repeated effects of hypoxia produce changes in the physiological reactions of the body directed toward better adaptation to changing gaseous environments.

Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis.

PubMed

Nguyen, Luan; Tao, Franklin Feng

2016-06-01

Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

Setting initial conditions for inflation with reaction-diffusion equation

NASA Astrophysics Data System (ADS)

Bagchi, Partha; Das, Arpan; Dave, Shreyansh S.; Sengupta, Srikumar; Srivastava, Ajit M.

2018-03-01

We discuss the issue of setting appropriate initial conditions for inflation. Specifically, we consider natural inflation model and discuss the fine tuning required for setting almost homogeneous initial conditions over a region of order several times the Hubble size which is orders of magnitude larger than any relevant correlation length for field fluctuations. We then propose to use the special propagating front solutions of reaction-diffusion equations for localized field domains of smaller sizes. Due to very small velocities of these propagating fronts we find that the inflaton field in such a field domain changes very slowly, contrary to naive expectation of rapid roll down to the true vacuum. Continued expansion leads to the energy density in the Hubble region being dominated by the vacuum energy, thereby beginning the inflationary phase. Our results show that inflation can occur even with a single localized field domain of size smaller than the Hubble size. We discuss possible extensions of our results for different inflationary models, as well as various limitations of our analysis (e.g. neglecting self gravity of the localized field domain).

Study of photosensitization reaction progress in a 96 well plate with photosensitizer rich condition using Talaporfin sodium

NASA Astrophysics Data System (ADS)

Ogawa, Emiyu; Takahashi, Mei; Arai, Tsunenori

2013-02-01

To quantitatively investigate photosensitization reaction in vitro against myocardial cells with photosensitizer rich condition in solution using Talaporfin sodium in the well of a 96 well plate, we studied photosensitization reaction progress in this well. We have proposed non-thermal conduction block of myocardium tissue using the photosensitization reaction with laser irradiation shortly after Talaporfin sodium injection. In above situation, the photosensitizer is located outside the myocardial cells in high concentration. To understand interaction of the photosensitization reaction in which the photosensitizer distributes outside cells, the photosensitization reaction progress in the well was studied. Talaporfin sodium (799.69 MW) solution and a 663 nm diode laser were used. The photosensitizer solution concentrations of 12.5-37.5 μM were employed. The photosensitizer fluorescence with 0.29 W/cm2 in irradiance, which was optimized in previous cell death study, was measured during the laser irradiation until 40 J/cm2. The photosensitizer solution absorbance and dissolved oxygen pressure after the laser irradiation were also measured. We found that the photosensitization reaction progress had 2 distinctive phases of different reaction rate: rapid photosensitization reaction consuming dissolved oxygen and gentle photosensitization reaction with oxygen diffusion from the solution-air boundary. The dissolved oxygen pressure and photosensitizer solution absorbance were 30% and 80% of the initial values after the laser irradiation, respectively. Therefore, oxygen was rate-controlling factor of the photosensitization reaction in the well with the photosensitizer rich condition. In the oxygen diffusion phase, the oxygen pressure was maintained around 40 mmHg until the laser irradiation of 40 J/cm2 and it is similar to that of myocardium tissue in vivo. We think that our 96 well plate in vitro system may simulate PDT in myocardial tissue with photosensitization reaction

Reaction of wood radius of multiple tree species to changing environmental conditions

NASA Astrophysics Data System (ADS)

Merganicova, Katarina; Merganic, Jan; Sitkova, Zuzana; Lestianska, Adriana; Strelcova, Katarina; Valent, Peter; Jezik, Marek

2017-04-01

Dendrometers are frequently used to study the radial dynamics of forest trees. Since the fluctuations of tree stem radius are caused by multiple factors including changes in tree water status and the actual tree growth, the methods used to derive the radial growth from dendrometer data provide us with the estimates of diurnal radial increments rather than their precise values. In addition, dendrometers react to environmental conditions themselves, which can in some cases cause misinterpretation of measured values. In the presented study we aimed at analysing the reaction of band dendrometers and wood radius of 7 different tree species on changing environmental conditions. The data come from a controlled experiment performed in the climate chambers, in which we placed 5 stand-alone dendrometers and 30 wooden pieces representing 7 different tree species equipped with band dendrometers. Air temperature and air humidity were controlled inside the chambers and their impact on wood radius and dendrometers was analysed. The results showed that both wooden pieces and dendrometers reacted to changes in air temperature and air humidity, while the reaction was species specific and dependent on the actual water status of wooden pieces. The overall trend of measured radial changes of wooden pieces followed the changes in temperature, i.e. the increase in temperature caused the increase in the measured radii. The change in air humidity explained less than 50% of the variation in radial measurements. The obtained results indicate that although the band dendrometers applied in the study were able to measure values with the precision of one micrometre, the differences between the measurements of up to ten micrometres need not represent the actual changes in stem radius, but may only reflect the reactions of the instrument to surrounding conditions. Hence, the measurements by dendrometers must always be examined thoroughly with regard to all the multiple effects before any

Determination of the in vivo NAD:NADH ratio in Saccharomyces cerevisiae under anaerobic conditions, using alcohol dehydrogenase as sensor reaction.

PubMed

Bekers, K M; Heijnen, J J; van Gulik, W M

2015-08-01

With the current quantitative metabolomics techniques, only whole-cell concentrations of NAD and NADH can be quantified. These measurements cannot provide information on the in vivo redox state of the cells, which is determined by the ratio of the free forms only. In this work we quantified free NAD:NADH ratios in yeast under anaerobic conditions, using alcohol dehydrogenase (ADH) and the lumped reaction of glyceraldehyde-3-phosphate dehydrogenase and 3-phosphoglycerate kinase as sensor reactions. We showed that, with an alternative accurate acetaldehyde determination method, based on rapid sampling, instantaneous derivatization with 2,4 diaminophenol hydrazine (DNPH) and quantification with HPLC, the ADH-catalysed oxidation of ethanol to acetaldehyde can be applied as a relatively fast and simple sensor reaction to quantify the free NAD:NADH ratio under anaerobic conditions. We evaluated the applicability of ADH as a sensor reaction in the yeast Saccharomyces cerevisiae, grown in anaerobic glucose-limited chemostats under steady-state and dynamic conditions. The results found in this study showed that the cytosolic redox status (NAD:NADH ratio) of yeast is at least one order of magnitude lower, and is thus much more reduced, under anaerobic conditions compared to aerobic glucose-limited steady-state conditions. The more reduced state of the cytosol under anaerobic conditions has major implications for (central) metabolism. Accurate determination of the free NAD:NADH ratio is therefore of importance for the unravelling of in vivo enzyme kinetics and to judge accurately the thermodynamic reversibility of each redox reaction. Copyright © 2015 John Wiley & Sons, Ltd.

Reaction time for trimolecular reactions in compartment-based reaction-diffusion models

NASA Astrophysics Data System (ADS)

Li, Fei; Chen, Minghan; Erban, Radek; Cao, Yang

2018-05-01

Trimolecular reaction models are investigated in the compartment-based (lattice-based) framework for stochastic reaction-diffusion modeling. The formulae for the first collision time and the mean reaction time are derived for the case where three molecules are present in the solution under periodic boundary conditions. For the case of reflecting boundary conditions, similar formulae are obtained using a computer-assisted approach. The accuracy of these formulae is further verified through comparison with numerical results. The presented derivation is based on the first passage time analysis of Montroll [J. Math. Phys. 10, 753 (1969)]. Montroll's results for two-dimensional lattice-based random walks are adapted and applied to compartment-based models of trimolecular reactions, which are studied in one-dimensional or pseudo one-dimensional domains.

MICROWAVE-ACCELERATED MULTICOMPONENT REACTIONS UNDER SOLVENT-FREE CONDITIONS

EPA Science Inventory

The application of microwave-accelerated solventless synthetic protocols in multicomponent (MCC) reactions will be exemplified by several condensation and cyclization reactions including the rapid one-pot assembly of valuable heterocyclic compounds from in situ generated intermed...

Thermonuclear reactions probed at stellar-core conditions with laser-based inertial-confinement fusion

DOE PAGES

Casey, D. T.; Sayre, D. B.; Brune, C. R.; ...

2017-08-07

Stars are giant thermonuclear plasma furnaces that slowly fuse the lighter elements in the universe into heavier elements, releasing energy, and generating the pressure required to prevent collapse. To understand stars, we must rely on nuclear reaction rate data obtained, up to now, under conditions very different from those of stellar cores. Here we show thermonuclear measurements of the 2H(d, n) 3He and 3H(t,2n) 4He S-factors at a range of densities (1.2–16 g cm –3) and temperatures (2.1–5.4 keV) that allow us to test the conditions of the hydrogen-burning phase of main-sequence stars. The relevant conditions are created using inertial-confinementmore » fusion implosions at the National Ignition Facility. Here, our data agree within uncertainty with previous accelerator-based measurements and establish this approach for future experiments to measure other reactions and to test plasma-nuclear effects present in stellar interiors, such as plasma electron screening, directly in the environments where they occur.« less

MICROWAVE-FACILITATED MULTICOMPONENT REACTIONS UNDER SOLVENT-FREE CONDITIONS

EPA Science Inventory

The application of microwave-expedited solvent-free synthetic protocols in multi-component (MCC) reactions will be exemplified by several condensation and cyclization reactions including the rapid one-pot assembly of heterocyclic compounds from in situ generated intermediates. R...

Impact of reaction conditions on grafting acrylamide onto starch

USDA-ARS?s Scientific Manuscript database

We have explored the radical initiated graft polymerization reaction of acrylamide onto starch where the solvent, concentration, temperature and reaction times were varied. We have found that the morphology of the resulting grafted polymer is dramatically different and is dependent on the reaction c...

Synthesis and Characterization of AlCl3 Impregnated Molybdenum Oxide as Heterogeneous Nano-Catalyst for the Friedel-Crafts Acylation Reaction in Ambient Condition.

PubMed

Jadhav, Arvind H; Chinnappan, Amutha; Hiremath, Vishwanath; Seo, Jeong Gil

2015-10-01

Aluminum trichloride (AlCl3) impregnated molybdenum oxide heterogeneous nano-catalyst was prepared by using simple impregnation method. The prepared heterogeneous catalyst was characterized by powder X-ray diffraction, FT-IR spectroscopy, solid-state NMR spectroscopy, SEM imaging, and EDX mapping. The catalytic activity of this protocol was evaluated as heterogeneous catalyst for the Friedel-Crafts acylation reaction at room temperature. The impregnated MoO4(AlCl2)2 catalyst showed tremendous catalytic activity in Friedel-Crafts acylation reaction under solvent-free and mild reaction condition. As a result, 84.0% yield of acyl product with 100% consumption of reactants in 18 h reaction time at room temperature was achieved. The effects of different solvents system with MoO4(AlCl2)2 catalyst in acylation reaction was also investigated. By using optimized reaction condition various acylated derivatives were prepared. In addition, the catalyst was separated by simple filtration process after the reaction and reused several times. Therefore, heterogeneous MoO4(AlCl2)2 catalyst was found environmentally benign catalyst, very convenient, high yielding, and clean method for the Friedel-Crafts acylation reaction under solvent-free and ambient reaction condition.

Preparation of ionic-crosslinked chitosan-based gel beads and effect of reaction conditions on drug release behaviors.

PubMed

Chen, Shilan; Liu, Mingzhu; Jin, Shuping; Wang, Bin

2008-02-12

Drug-loaded chitosan (CS) beads were prepared under simple and mild condition using trisodium citrate as ionic crosslinker. The beads were further coated with poly(methacrylic acid) (PMAA) by dipping the beads in PMAA aqueous solution. The surface and cross-section morphology of these beads were observed by scanning electron microscopy and the observation showed that the coating beads had core-shell structure. In vitro release of model drug from these beads obtained under different reaction conditions was investigated in buffer medium (pH 1.8). The results showed that the rapid drug release was restrained by PMAA coating and the optimum conditions for preparing CS-based drug-loaded beads were decided through the effect of reaction conditions on the drug release behaviors. In addition, the drug release mechanism of CS-based drug-loaded beads was analyzed by Peppa's potential equation. According to this study, the ionic-crosslinked CS beads coated by PMAA could serve as suitable candidate for drug site-specific carrier in stomach.

Tribological reactions of perfluoroalkyl polyether oils with stainless steel under ultrahigh vacuum conditions at room temperature

NASA Technical Reports Server (NTRS)

Mori, Shigeyuki; Morales, Wilfredo

1989-01-01

The reaction between three types of commercial perfluoroalkyl polyether (PFPE) oils and stainless steel 440C was investigated experimentally during sliding under ultrahigh vacuum conditions at room temperature. It is found that the tribological reaction of PFPE is mainly affected by the activity of the mechanically formed fresh surfaces of metals rather than the heat generated at the sliding contacts. The fluorides formed on the wear track act as a boundary layer, reducing the friction coefficient.

Supervisors' attitudes and skills for active listening with regard to working conditions and psychological stress reactions among subordinate workers.

PubMed

Mineyama, Sachiko; Tsutsumi, Akizumi; Takao, Soshi; Nishiuchi, Kyoko; Kawakami, Norito

2007-03-01

We investigated whether supervisors' listening attitudes and skills were related to working conditions and psychological stress reactions among their subordinates. The subjects included 41 male supervisors and their immediate subordinates (n=203). The supervisors completed a short version of the Active Listening Attitude Scale (ALAS) consisting of two subscales: Listening Attitude and Listening Skill for Active Listening. The subordinates rated working conditions and their psychological stress reactions using selected scales of the Job Content Questionnaire and the Brief Job Stress Questionnaire. Those subordinates who worked under supervisors with a higher score of Listening Attitude and Listening Skill reported a more favorable psychological stress reaction than those who worked under supervisors with a lower score of Listening Attitude and Listening Skill. Those subordinates who worked under supervisors with a higher score of Listening Skill reported higher worksite support than those who worked under supervisors with a lower score of Listening Skill. Those subordinates who worked under supervisors with a higher score of Listening Attitude reported higher job control than those who worked under supervisors with a lower score of Listening Attitude. A supervisor's listening attitude and skill appeared to affect psychological stress reactions predominantly among male subordinates than among female subordinates. Psychological stress reactions were lower among younger subordinates who worked under supervisors with high listening skill, while no statistically difference was observed among older subordinates. These findings suggest that a supervisor's listening attitude and skill have an effect on working conditions and psychological stress reactions among subordinates and that the effects vary according to the subordinates' sex and age.

Reaction to frustration in high and low feather pecking lines of laying hens from commercial or semi-natural rearing conditions.

PubMed

Rodenburg, T B; Koene, P; Spruijt, B M

2004-02-27

The effect of rearing conditions on feather pecking and reaction to frustration was studied in two lines of laying hens. From commercial rearing conditions (large group, no mother hen), seven birds from a high feather pecking line (HC birds) and eight birds from a low feather pecking line (LC birds) were used. From semi-natural rearing conditions (small group, mother hen present) seven birds from the high feather pecking line (HN birds) were used. Feather pecking behaviour of HC, LC, and HN groups was recorded for 30 min. After that, each bird was food deprived and trained to peck a key for a food reward in a Skinnerbox. After training, each bird was subjected to a frustration session in a Skinnerbox, where the feeder was covered with Perspex. Three HC birds showed severe feather pecking, compared with one HN bird and zero LC birds. Differences in reaction to frustration were found between birds from different lines, but not in birds from different rearing conditions. LC birds tended to put their head in the feeder more frequently than HC birds over all sessions. Although limited, this study indicates that rearing conditions influence feather pecking, but not reaction to frustration.

Method and apparatus for measuring coupled flow, transport, and reaction processes under liquid unsaturated flow conditions

DOEpatents

McGrail, Bernard P.; Martin, Paul F.; Lindenmeier, Clark W.

1999-01-01

The present invention is a method and apparatus for measuring coupled flow, transport and reaction processes under liquid unsaturated flow conditions. The method and apparatus of the present invention permit distinguishing individual precipitation events and their effect on dissolution behavior isolated to the specific event. The present invention is especially useful for dynamically measuring hydraulic parameters when a chemical reaction occurs between a particulate material and either liquid or gas (e.g. air) or both, causing precipitation that changes the pore structure of the test material.

Factors that condition the spontaneous reporting of adverse drug reactions among nurses: an integrative review.

PubMed

De Angelis, Alessia; Colaceci, Sofia; Giusti, Angela; Vellone, Ercole; Alvaro, Rosaria

2016-03-01

To describe and synthesise previous research on factors conditioning the spontaneous reporting of adverse drug reactions among nurses. Spontaneous reports of adverse drug reactions by health-care providers, are a main instrument for the continuous evaluation of the risk-benefit ratio of every drug. Under-reporting of adverse drug reactions by all health-care providers, in particular by nurses, is a major limitation to this system. An integrated review of the literature was conducted using MEDLINE, CINAHL, Embase, Scopus databases and Google Scholar. After evaluation for appropriateness related to inclusion/exclusion criteria, 16 studies were included in the final analysis and synthesis. Two factors emerged from the study: (1) intrinsic factors related to nurses' knowledge and attitudes; (2) extrinsic factors related to nurses' interaction with health-care organisations and to the relationship between nurses and physicians. Nurses' attitudes that hinder reporting include ignorance, insecurity, fear and lethargy. Nurses are not fully aware of their role in adverse drug reaction reporting. Nurses must acquire greater knowledge to implement specific skills into their daily clinical practice. To improve nurses' reporting of adverse drug reactions, it is necessary to develop management approaches that modify both intrinsic and extrinsic factors. © 2015 John Wiley & Sons Ltd.

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.

Sensory characteristics and consumer acceptability of beef stock containing glutathione Maillard reaction products prepared at various conditions.

PubMed

Kwon, G Y; Hong, J H; Kim, Y S; Lee, S M; Kim, K O

2011-01-01

The sensory characteristics and consumer acceptability of beef soup samples containing 9 types of glutathione Maillard reaction products (GMRPs) were investigated to examine the effects of the GMRPs produced under different reaction conditions on the flavor of the beef soup. The sensory characteristics of the beef stocks were examined using descriptive analysis. In consumer testing, 50 consumers evaluated the overall acceptability and flavor intensities of beef odor, salty taste, beef flavor, and seasoning flavor in the beef soup samples. It was found that the reaction conditions, including sugar type and pH, affected the sensory characteristics of the beef stock containing the GMRPs. The samples containing the GMRPs reacted at pH 7 were characterized with strong beef flavor, chestnut flavor, and cooked rice flavor. However, the GMRP reacted with xylose at pH 7 (XM7) was significantly stronger in beef-related sensory characteristics than the GMRPs reacted with glucose or fructose at pH 7 (GM7 and FM7). The samples containing the GMRPs reacted at pH 3 had strong acid-related attributes whereas the GMRPs reacted at pH 11 exhibited strong sulfur-related attributes and a bitter taste. Overall, the beef soup containing XM7, which was perceived as having a strong beef odor and flavor, was rated the highest consumer acceptability score. This suggests that XM7 has feasibility as a flavor enhancer. To elucidate its effectiveness further, it is required to apply XM7 in various food systems at varying levels and to compare its flavor enhancing effects with other flavor enhancers such as monosodium L-glutamate in future studies. Practical Application: This study characterized sensory attributes of glutathione Maillard reaction products (GMRPs) reacted under various conditions and evaluated their potential as a flavor enhancer by examining consumer acceptability of beef stock containing the GMRPs. This study showed that the GMRP reacted with xylose at pH 7 had strong 71 beef

The photochemical reaction of hydrocarbons under extreme thermobaric conditions

NASA Astrophysics Data System (ADS)

Serovaiskii, Aleksandr; Kolesnikov, Anton; Mukhina, Elena; Kutcherov, Vladimir

2017-10-01

The photochemical reaction of hydrocarbons was found to play an important role in the experiments with the synthetic petroleum conducted in Diamond Anvil Cell (DAC). Raman spectroscopy with a green laser (514.5 nm) was used for in situ sample analysis. This photochemical effect was investigated in the pressure range of 0.7-5 GPa, in the temperature interval from the ambient conditions to 450°C. The power of laser used in these experiment series was from 0.05 W to 0.6 W. The chemical transformation was observed when the necessary threshold pressure (~2.8 GPa) was reached. This transformation correlated with the luminescence appearance on the Raman spectra and a black opaque spot in the sample was observed in the place where the laser focus was forwarded. The exposure time and laser power (at least in the 0.1-0.5 W range) did not play a role in the 0.1-0.5 GPa range.

A Novel Endo-β-N-Acetylglucosaminidase Releases Specific N-Glycans Depending on Different Reaction Conditions

PubMed Central

De Moura Bell, Juliana Maria Leite Nobrega; Frese, Steven A.; Liu, Yan; Mills, David A.; Block, David E.; Barile, Daniela

2015-01-01

Milk glycoproteins are involved in different functions and contribute to different cellular processes, including adhesion and signaling, and shape the development of the infant micro-biome. Methods have been developed to study the complexities of milk protein glycosylation and understand the role of N-glycans in protein functionality. Endo-β-N-acetylglucosaminidase (EndoBI-1) isolated from Bifidobacterium longum subsp. infantis ATCC 15697 is a recently isolated heat-stable enzyme that cleaves the N-N′-diacetyl chitobiose moiety found in the N-glycan core. The effects of different processing conditions (pH, temperature, reaction time, and enzyme/protein ratio) were evaluated for their ability to change EndoBI-1 activity on bovine colostrum whey glycoproteins using advanced mass spectrometry. This study shows that EndoBI-1 is able to cleave a high diversity of N-glycan structures. Nano-LC-Chip–Q-TOF MS data also revealed that different reaction conditions resulted in different N-glycan compositions released, thus modifying the relative abundance of N-glycan types. In general, more sialylated N-glycans were released at lower temperatures and pH values. These results demonstrated that EndoBI-1 is able to release a wide variety of N-glycans, whose compositions can be selectively manipulated using different processing conditions. PMID:26101185

Contribution of Histidine and Lysine to the Generation of Volatile Compounds in Jinhua Ham Exposed to Ripening Conditions Via Maillard Reaction.

PubMed

Zhu, Chao-Zhi; Zhao, Jing-Li; Tian, Wei; Liu, Yan-Xia; Li, Miao-Yun; Zhao, Gai-Ming

2018-01-01

To evaluate the role of Maillard reactions in the generation of flavor compounds in Jinhua ham, the reactions of glucose and ethanal with histidine and lysine, respectively, were studied by simulating the ripening conditions of Jinhua ham. The volatile products produced were analyzed using solid phase microextraction-gas chromatography/mass spectrometry. The results showed that 8 volatile compounds were generated by the reaction of glucose and histidine and 10 volatile compounds were generated by the reaction of glucose and lysine. Reactions of ethanal with lysine and with histidine both generated 31 volatile compounds that contributed to the flavor of Jinhua ham. This indicates that histidine and lysine related to Maillard reactions possibly play important roles in the generation of the unique flavor compounds in Jinhua ham. This research demonstrates that free amino acids participate in the generation of volatile compounds from Jinhua ham via the Maillard reaction and provides a basic mechanism to explain flavor formation in Jinhua ham. Jinhua ham is a well-known traditional Chinese dry-cured meat product. However, the formation of the compounds comprising its special flavor is not well understood. Our results indicate that Maillard reactions occur in Jinhua ham under ripening conditions. This work illustrates the contribution of Maillard reactions to the flavor of Jinhua ham. © 2017 Institute of Food Technologists®.

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.

Exploring Reaction Conditions to Improve the Magnetic Response of Cobalt-Doped Ferrite Nanoparticles

PubMed Central

Galarreta, Itziar; Gil de Muro, Izaskun; Lezama, Luis

2018-01-01

With the aim of studying the influence of synthesis parameters in structural and magnetic properties of cobalt-doped magnetite nanoparticles, Fe3−xCoxO4 (0 < x < 0.15) samples were synthetized by thermal decomposition method at different reaction times (30–120 min). The Co ferrite nanoparticles are monodisperse with diameters between 6 and 11 nm and morphologies depending on reaction times, varying from spheric, cuboctahedral, to cubic. Chemical analysis and X-ray diffraction were used to confirm the composition, high crystallinity, and pure-phase structure. The investigation of the magnetic properties, both magnetization and electronic magnetic resonance, has led the conditions to improve the magnetic response of doped nanoparticles. Magnetization values of 86 emu·g−1 at room temperature (R.T.) have been obtained for the sample with the highest Co content and the highest reflux time. Magnetic characterization also displays a dependence of the magnetic anisotropy constant with the varying cobalt content. PMID:29370104

Multi-component Fe–Ni hydroxide nanocatalyst for oxygen evolution and methanol oxidation reactions under alkaline conditions

DOE PAGES

Candelaria, Stephanie L.; Bedford, Nicholas M.; Woehl, Taylor J.; ...

2016-11-29

Here, iron-incorporated nickel-based materials show promise as catalysts for the oxygen evolution reac-tion (OER) half-reaction of water electrolysis. Nickel has also exhibited high catalytic activity for methanol oxidation, particularly when in the form of a bimetallic catalyst. In this work, bimetallic iron-nickel nanoparticles were synthesized using a multi-step procedure in water under ambient conditions. When compared to monometallic iron and nickel nanoparticles, Fe-Ni nanoparticles show enhanced catalytic activity for both OER and methanol oxidation under alkaline conditions. At 1 mA/cm 2, the overpotential for monometallic iron and nickel nanoparticles was 421 mV and 476 mV, respectively, while the bimetallic Fe-Nimore » nanoparticles had a greatly reduced overpotential of 256 mV. At 10 mA/cm 2, bimetallic Fe-Ni nanoparticles had an overpotential of 311 mV. Spec-troscopy characterization suggests that the primary phase of nickel in Fe-Ni nanoparticles is the more disordered alpha phase of nickel hydroxide.« less

Reaction of perfluoroalkylpolyethers (PFPE) with 440C steel in vacuum under sliding conditions at room temperature

NASA Technical Reports Server (NTRS)

Mori, Shigeyuki; Morales, Wilfredo

1989-01-01

Reactions of perfluoroalkylpolyethers (PFPE: Fomblin, Demnum and Krytox) were studied during the sliding contact of stainless steel specimens under ultrahigh vacuum conditions. All three fluids reacted with the steel specimens during sliding. Fomblin, which has acetal linkages, decomposed under the sliding conditions generating gaseous products, (COF2 and fluorinated carbons) which were detected by a quadrupole mass spectrometer. Gaseous products were not detected for the Demnum and Krytox fluids. The amount of gaseous products from Fomblin increased with increasing sliding speed. At the end of the sliding experiments, the wear scar and deposits on the specimens were examined by small spot size XPS. The oxide layer on the specimen surface was removed during sliding, and metal fluorides were formed on the worn surface. The surface of the wear scar and deposits were covered with adsorbed PFPE. Based on these results, it was concluded that the decomposition reaction on Fomblin was initiated by contacting the fluid with a fresh metal surface which was formed during sliding.

Optimisation of the reaction conditions for the production of cross-linked starch with high resistant starch content.

PubMed

Kahraman, Kevser; Koksel, Hamit; Ng, Perry K W

2015-05-01

The optimum reaction conditions (temperature and pH) for the preparation of cross-linked (CL) corn and wheat starches with maximum resistant starch (RS) content were investigated by using response surface methodology (RSM). According to the preliminary results, five levels were selected for reaction temperature (38-70 °C) and pH (10-12) in the main study. RS contents of the CL corn and wheat starch samples increased with increasing temperature and pH, and pH had a greater influence on RS content than had temperature. The maximum RS content (with a maximum p value of 0.4%) was obtained in wheat starch cross-linked at 38 °C and pH 12. In the case of CL corn starch, the optimum condition was 70 °C and pH 12. CL corn and wheat starch samples were also produced separately under the optimum conditions and their RS contents were 80.4% and 83.9%, respectively. These results were also in agreement with the values predicted by RSM. Copyright © 2014 Elsevier Ltd. All rights reserved.

Rock-fluid chemical interactions at reservoir conditions: The influence of brine chemistry and extent of reaction

NASA Astrophysics Data System (ADS)

Anabaraonye, B. U.; Crawshaw, J.; Trusler, J. P. M.

2016-12-01

Following carbon dioxide injection in deep saline aquifers, CO2 dissolves in the formation brines forming acidic solutions that can subsequently react with host reservoir minerals, altering both porosity and permeability. The direction and rates of these reactions are influenced by several factors including properties that are associated with the brine system. Consequently, understanding and quantifying the impacts of the chemical and physical properties of the reacting fluids on overall reaction kinetics is fundamental to predicting the fate of the injected CO2. In this work, we present a comprehensive experimental study of the kinetics of carbonate-mineral dissolution in different brine systems including sodium chloride, sodium sulphate and sodium bicarbonate of varying ionic strengths. The impacts of the brine chemistry on rock-fluid chemical reactions at different extent of reactions are also investigated. Using a rotating disk technique, we have investigated the chemical interactions between the CO2-saturated brines and carbonate minerals at conditions of pressure (up to 10 MPa) and temperature (up to 373 K) pertinent to carbon storage. The changes in surface textures due to dissolution reaction were studied by means of optical microscopy and vertical scanning interferometry. Experimental results are compared to previously derived models.

An effective rate equation approach to reaction kinetics in small volumes: theory and application to biochemical reactions in nonequilibrium steady-state conditions.

PubMed

Grima, R

2010-07-21

Chemical master equations provide a mathematical description of stochastic reaction kinetics in well-mixed conditions. They are a valid description over length scales that are larger than the reactive mean free path and thus describe kinetics in compartments of mesoscopic and macroscopic dimensions. The trajectories of the stochastic chemical processes described by the master equation can be ensemble-averaged to obtain the average number density of chemical species, i.e., the true concentration, at any spatial scale of interest. For macroscopic volumes, the true concentration is very well approximated by the solution of the corresponding deterministic and macroscopic rate equations, i.e., the macroscopic concentration. However, this equivalence breaks down for mesoscopic volumes. These deviations are particularly significant for open systems and cannot be calculated via the Fokker-Planck or linear-noise approximations of the master equation. We utilize the system-size expansion including terms of the order of Omega(-1/2) to derive a set of differential equations whose solution approximates the true concentration as given by the master equation. These equations are valid in any open or closed chemical reaction network and at both the mesoscopic and macroscopic scales. In the limit of large volumes, the effective mesoscopic rate equations become precisely equal to the conventional macroscopic rate equations. We compare the three formalisms of effective mesoscopic rate equations, conventional rate equations, and chemical master equations by applying them to several biochemical reaction systems (homodimeric and heterodimeric protein-protein interactions, series of sequential enzyme reactions, and positive feedback loops) in nonequilibrium steady-state conditions. In all cases, we find that the effective mesoscopic rate equations can predict very well the true concentration of a chemical species. This provides a useful method by which one can quickly determine the

Hot-Fire Testing of 100 LB(sub F) LOX/LCH4 Reaction Control Engine at Altitude Conditions

NASA Technical Reports Server (NTRS)

Marshall, William M.; Kleinhenz, Julie E.

2010-01-01

Liquid oxygen/liquid methane (LO2/LCH4 ) has recently been viewed as a potential green propulsion system for both the Altair ascent main engine (AME) and reaction control system (RCS). The Propulsion and Cryogenic Advanced Development Project (PCAD) has been tasked by NASA to develop these green propellant systems to enable safe and cost effective exploration missions. However, experience with LO2/LCH4 as a propellant combination is limited, so testing of these systems is critical to demonstrating reliable ignition and performance. A test program of a 100 lb f reaction control engine (RCE) is underway at the Altitude Combustion Stand (ACS) of the NASA Glenn Research Center, with a focus on conducting tests at altitude conditions. These tests include a unique propellant conditioning feed system (PCFS) which allows for the inlet conditions of the propellant to be varied to test warm to subcooled liquid propellant temperatures. Engine performance, including thrust, c* and vacuum specific impulse (I(sub sp,vac)) will be presented as a function of propellant temperature conditions. In general, the engine performed as expected, with higher performance at warmer propellant temperatures but better efficiency at lower propellant temperatures. Mixture ratio effects were inconclusive within the uncertainty bands of data, but qualitatively showed higher performance at lower ratios.

A proposed abiotic reaction scheme for hydroxylamine and monochloramine under chloramination relevant drinking water conditions.

PubMed

Wahman, David G; Speitel, Gerald E; Machavaram, Madhav V

2014-09-01

Drinking water monochloramine (NH2Cl) use may promote ammonia-oxidizing bacteria (AOB). AOB use (i) ammonia monooxygenase for biological ammonia (NH3) oxidation to hydroxylamine (NH2OH) and (ii) hydroxylamine oxidoreductase for NH2OH oxidation to nitrite. NH2Cl and NH2OH may react, providing AOB potential benefits and detriments. The NH2Cl/NH2OH reaction would benefit AOB by removing the disinfectant (NH2Cl) and releasing their growth substrate (NH3), but the NH2Cl/NH2OH reaction would also provide a possible additional inactivation mechanism besides direct NH2Cl reaction with cells. Because biological NH2OH oxidation supplies the electrons required for biological NH3 oxidation, the NH2Cl/NH2OH reaction provides a direct mechanism for NH2Cl to inhibit NH3 oxidation, starving the cell of reductant by preventing biological NH2OH oxidation. To investigate possible NH2Cl/NH2OH reaction implications on AOB, an understanding of the underlying abiotic reaction is first required. The present study conducted a detailed literature review and proposed an abiotic NH2Cl/NH2OH reaction scheme (RS) for chloramination relevant drinking water conditions (μM concentrations, air saturation, and pH 7-9). Next, RS literature based kinetics and end-products were evaluated experimentally between pHs 7.7 and 8.3, representing (i) the pH range for future experiments with AOB and (ii) mid-range pHs typically found in chloraminated drinking water. In addition, a (15)N stable isotope experiment was conducted to verify nitrous oxide and nitrogen gas production and their nitrogen source. Finally, the RS was slightly refined using the experimental data and an AQUASIM implemented kinetic model. A chloraminated drinking water relevant RS is proposed and provides the abiotic reaction foundation for future AOB biotic experiments. Published by Elsevier Ltd.

A heterobimetallic complex featuring a Ti–Co multiple bond and its application to the reductive coupling of ketones to alkenes† †Electronic supplementary information (ESI) available: Experimental procedures, additional spectroscopic data for 1–4, and computational details of 2 and 3. CCDC 1037714–1037716. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc03772c Click here for additional data file. Click here for additional data file.

PubMed Central

Wu, Bing; Bezpalko, Mark W.; Foxman, Bruce M.

2015-01-01

To explore metal–metal multiple bonds between first row transition metals, Ti/Co complexes supported by two phosphinoamide ligands have been synthesized and characterized. The Ti metalloligand Cl2Ti(XylNPiPr2)2 (1) was treated with CoI2 under reducing conditions, permitting isolation of the Ti/Co complex [(μ-Cl)Ti(XylNPiPr2)2CoI]2 (2). One electron reduction of complex 2 affords ClTi(XylNPiPr2)2CoPMe3 (3), which features a metal–metal triple bond and an unprecedentedly short Ti–Co distance of 2.0236(9) Å. This complex is shown to promote the McMurry coupling reaction of aryl ketones into alkenes, with concomitant formation of the tetranuclear complex [Ti(μ3-O)(NXylPiPr2)2CoI]2 (4). A cooperative mechanism involving bimetallic C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 O bond activation and a cobalt carbene intermediate is

Two Macrocycles in One Shot: Synthesis, Spectroscopy, Photophysics, and Tautomerism of 23-Oxahemiporphycene and 21-Oxacorrole-5-carbaldehyde.

PubMed

Ostapko, Jakub; Kelm, Anna; Kijak, Michał; Leśniewska, Barbara; Waluk, Jacek

2018-04-19

The synthesis of 23-oxahemiporphycene, the first monooxa analogue of hemiporphycene, a structural isomer of porphyrin, is reported. Its generation under McMurry reaction conditions is surprisingly accompanied by the appearance of a formyl derivative of oxacorrole, 21-oxacorrole-5-carbaldehyde. A mechanism for the formation of the latter is proposed, relying on pinacol rearrangement of titanium pinacolate. The structures of the most stable tautomeric forms are established for both compounds based on IR and NMR spectra combined with DFT calculations. Spectral and photophysical characteristics are compared with those of structurally similar macrocycles. Replacement of one nitrogen by oxygen in hemiporphycene has only a minor impact. In contrast, for corrole it leads to the enhancement of stability and to strongly reduced rates of nonradiative deactivation of the lowest excited singlet state. This is explained by the planarity of oxacorroles, achieved by removing one of the inner hydrogen atoms from the inner cavity. Unusual crystal packing is observed for the protonated form of 23-oxahemiporphycene, which exhibits a π-π stacked columnar alignment of positively charged macrocycle units. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Concordant Chemical Reaction Networks and the Species-Reaction Graph

PubMed Central

Shinar, Guy; Feinberg, Martin

2015-01-01

In a recent paper it was shown that, for chemical reaction networks possessing a subtle structural property called concordance, dynamical behavior of a very circumscribed (and largely stable) kind is enforced, so long as the kinetics lies within the very broad and natural weakly monotonic class. In particular, multiple equilibria are precluded, as are degenerate positive equilibria. Moreover, under certain circumstances, also related to concordance, all real eigenvalues associated with a positive equilibrium are negative. Although concordance of a reaction network can be decided by readily available computational means, we show here that, when a nondegenerate network’s Species-Reaction Graph satisfies certain mild conditions, concordance and its dynamical consequences are ensured. These conditions are weaker than earlier ones invoked to establish kinetic system injectivity, which, in turn, is just one ramification of network concordance. Because the Species-Reaction Graph resembles pathway depictions often drawn by biochemists, results here expand the possibility of inferring significant dynamical information directly from standard biochemical reaction diagrams. PMID:22940368

Housing conditions influence cortical and behavioural reactions of sheep in response to videos showing social interactions of different valence.

PubMed

Vögeli, Sabine; Wolf, Martin; Wechsler, Beat; Gygax, Lorenz

2015-05-01

Mood, as a long-term affective state, is thought to modulate short-term emotional reactions in animals, but the details of this interplay have hardly been investigated experimentally. Apart from a basic interest in this affective system, mood is likely to have an important impact on animal welfare, as bad mood may taint all emotional experience. In the present study about mood - emotion interaction, 29 sheep were kept under predictable, stimulus-rich or unpredictable, stimulus-poor housing conditions, to induce different mood states. In an experiment, the animals were confronted with video sequences of social interactions of conspecifics showing agonistic interactions, ruminating or tolerantly co-feeding as stimuli of different valences. Emotional reactions were assessed by measuring frontal brain activity using functional near-infrared spectroscopy and by recording behavioral reactions. Attentiveness of the sheep decreased from videos showing agonistic interactions to ruminating sheep to those displaying co-feeding sheep. Seeing agonistic interactions was also associated with a deactivation of the frontal cortex, specifically in animals living under predictable, stimulus-rich housing conditions. These sheep generally showed less attentiveness and locomotor activity and they had their ears in a forward position less often and in a backward position more often than the sheep from the unpredictable, stimulus-poor conditions. Housing conditions influenced how the sheep behaved, which can either be thought to be mediated by mood or by the animals' previous experience with stimulus-richness in their housing conditions. Frontal cortical activity may not depend on valence only, but also on the perceptual channel through which the stimuli were perceived. Copyright © 2015 Elsevier B.V. All rights reserved.

In situ characterization of catalysts and membranes in a microchannel under high-temperature water gas shift reaction conditions

NASA Astrophysics Data System (ADS)

Cavusoglu, G.; Dallmann, F.; Lichtenberg, H.; Goldbach, A.; Dittmeyer, R.; Grunwaldt, J.-D.

2016-05-01

Microreactor technology with high heat transfer in combination with stable catalysts is a very attractive approach for reactions involving major heat effects such as methane steam reforming and to some extent, also the high temperature water gas shift (WGS) reaction. For this study Rh/ceria catalysts and an ultrathin hydrogen selective membrane were characterized in situ in a microreactor specially designed for x-ray absorption spectroscopic measurements under WGS conditions. The results of these experiments can serve as a basis for further development of the catalysts and membranes.

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.

The use of a microreactor for rapid screening of the reaction conditions and investigation of the photoluminescence mechanism of carbon dots.

PubMed

Lu, Yue; Zhang, Ling; Lin, Hengwei

2014-04-07

A microreactor is applied and reported, for the first time, in the field of research of carbon dots (CDs), including rapid screening of the reaction conditions and investigation of the photoluminescence (PL) mechanism. Various carbonaceous precursors and solvents were selected and hundreds of reaction conditions were screened (ca. 15 min on average per condition). Through analyzing the screened conditions, tunable PL emission maxima, from about 330 to 550 nm with respectable PL quantum yields, were achieved. Moreover, the relationship between different developmental stages of the CDs and the PL properties was explored by using the microreactor. The PL emission was observed to be independent of the composition, carbonization extent, and morphology/size of the CDs. This study unambiguously presents that a microreactor could serve as a promising tool for the research of CDs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Knoevenagel Initiated Annulation Reaction Using Room Temperature or Microwave Conditions

ERIC Educational Resources Information Center

Cook, A. Gilbert

2007-01-01

An experiment is presented that has the student execute a Knoevenagel initiated annulation reaction. The reaction can be carried out either through use of a microwave reactor or by allowing the mixture to stand at room temperature for two days. The student is then challenged to identify the reaction product through a guided prelab exercise of the…

Optimizing Chemical Reactions with Deep Reinforcement Learning.

PubMed

Zhou, Zhenpeng; Li, Xiaocheng; Zare, Richard N

2017-12-27

Deep reinforcement learning was employed to optimize chemical reactions. Our model iteratively records the results of a chemical reaction and chooses new experimental conditions to improve the reaction outcome. This model outperformed a state-of-the-art blackbox optimization algorithm by using 71% fewer steps on both simulations and real reactions. Furthermore, we introduced an efficient exploration strategy by drawing the reaction conditions from certain probability distributions, which resulted in an improvement on regret from 0.062 to 0.039 compared with a deterministic policy. Combining the efficient exploration policy with accelerated microdroplet reactions, optimal reaction conditions were determined in 30 min for the four reactions considered, and a better understanding of the factors that control microdroplet reactions was reached. Moreover, our model showed a better performance after training on reactions with similar or even dissimilar underlying mechanisms, which demonstrates its learning ability.

Reaction Kinetic Model of Dilute Acid-Catalyzed Hemicellulose Hydrolysis of Corn Stover under High-Solid Conditions

DOE PAGES

Shi, Suan; Guan, Wenjian; Kang, Li; ...

2017-09-13

High solid conditions are desirable in pretreatment of lignocellulosic biomass. An advanced dilute-acid pretreatment reactor has been developed at National Renewable Energy Laboratory (NREL). It is a continuous auger-driven reactor that can be operated with high-solid charge at high temperature and with short residence time resulting high productivity and high sugar concentration. Here, we investigated the kinetics of the reactions associated with dilute-acid pretreatment of corn stover, covering the reaction conditions of the NREL reactor operation: 155-185 C, 1-2 wt% sulfuric acid concentration, and 1:2 solid to liquid ratio. The experimental data were fitted to a first-order biphasic model whichmore » assumes that xylan is comprised of two different fragments: fast and slow reacting fractions. Due to the high solid loading condition, significant amount of xylose oligomers was observed during the pretreatment. We also included the oligomers as an intermediate entity in the kinetic model. The effect of acid concentration was incorporated into the pre-exponential factor of Arrhenius equation. The kinetic model with bestfit kinetic parameters has shown good agreement with experimental data. The kinetic parameter values of the proposed model were noticeably different from those previously reported. The activation energies of xylan hydrolysis are lower and the acid exponents are higher than the average of literature values. The proposed model can serve as a useful tool for design and operation of pretreatment system pertaining to corn stover.« less

Reaction Kinetic Model of Dilute Acid-Catalyzed Hemicellulose Hydrolysis of Corn Stover under High-Solid Conditions

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

Shi, Suan; Guan, Wenjian; Kang, Li

High solid conditions are desirable in pretreatment of lignocellulosic biomass. An advanced dilute-acid pretreatment reactor has been developed at National Renewable Energy Laboratory (NREL). It is a continuous auger-driven reactor that can be operated with high-solid charge at high temperature and with short residence time resulting high productivity and high sugar concentration. Here, we investigated the kinetics of the reactions associated with dilute-acid pretreatment of corn stover, covering the reaction conditions of the NREL reactor operation: 155-185 C, 1-2 wt% sulfuric acid concentration, and 1:2 solid to liquid ratio. The experimental data were fitted to a first-order biphasic model whichmore » assumes that xylan is comprised of two different fragments: fast and slow reacting fractions. Due to the high solid loading condition, significant amount of xylose oligomers was observed during the pretreatment. We also included the oligomers as an intermediate entity in the kinetic model. The effect of acid concentration was incorporated into the pre-exponential factor of Arrhenius equation. The kinetic model with bestfit kinetic parameters has shown good agreement with experimental data. The kinetic parameter values of the proposed model were noticeably different from those previously reported. The activation energies of xylan hydrolysis are lower and the acid exponents are higher than the average of literature values. The proposed model can serve as a useful tool for design and operation of pretreatment system pertaining to corn stover.« less

A study of different indicators of Maillard reaction with whey proteins and different carbohydrates under adverse storage conditions.

PubMed

Leiva, Graciela E; Naranjo, Gabriela B; Malec, Laura S

2017-01-15

This study examined different indicators of each stage of Maillard reaction under adverse storage conditions in a system with whey proteins and lactose or glucose. The analysis of lysine loss by the o-phthaldialdehyde method can be considered a good indicator of the early stage, showing considerable differences in reactivity when systems with mono and disaccharides were analyzed. Capillary electrophoresis proved to be a sensitive method for evaluating the extent of glycosylation of the native proteins, providing valuable information when the loss of lysine was not significant. The estimation of the Amadori compound from the determination of total 5-hydroxymethyl-2-furfuraldehyde would have correlate well with reactive lysine content if the advanced stages of the reaction had not been reached. For assessing the occurrence of the intermediate and final stages, the measurement of free 5-hydroxymethyl-2-furfuraldehyde and color, proved not to be suitable for storage conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Population dynamics, information transfer, and spatial organization in a chemical reaction network under spatial confinement and crowding conditions

NASA Astrophysics Data System (ADS)

Bellesia, Giovanni; Bales, Benjamin B.

2016-10-01

We investigate, via Brownian dynamics simulations, the reaction dynamics of a generic, nonlinear chemical network under spatial confinement and crowding conditions. In detail, the Willamowski-Rossler chemical reaction system has been "extended" and considered as a prototype reaction-diffusion system. Our results are potentially relevant to a number of open problems in biophysics and biochemistry, such as the synthesis of primitive cellular units (protocells) and the definition of their role in the chemical origin of life and the characterization of vesicle-mediated drug delivery processes. More generally, the computational approach presented in this work makes the case for the use of spatial stochastic simulation methods for the study of biochemical networks in vivo where the "well-mixed" approximation is invalid and both thermal and intrinsic fluctuations linked to the possible presence of molecular species in low number copies cannot be averaged out.

Optimizing Chemical Reactions with Deep Reinforcement Learning

PubMed Central

2017-01-01

Deep reinforcement learning was employed to optimize chemical reactions. Our model iteratively records the results of a chemical reaction and chooses new experimental conditions to improve the reaction outcome. This model outperformed a state-of-the-art blackbox optimization algorithm by using 71% fewer steps on both simulations and real reactions. Furthermore, we introduced an efficient exploration strategy by drawing the reaction conditions from certain probability distributions, which resulted in an improvement on regret from 0.062 to 0.039 compared with a deterministic policy. Combining the efficient exploration policy with accelerated microdroplet reactions, optimal reaction conditions were determined in 30 min for the four reactions considered, and a better understanding of the factors that control microdroplet reactions was reached. Moreover, our model showed a better performance after training on reactions with similar or even dissimilar underlying mechanisms, which demonstrates its learning ability. PMID:29296675

Materials and Mechanisms of Photo-Assisted Chemical Reactions under Light and Dark Conditions: Can Day-Night Photocatalysis Be Achieved?

PubMed

Sakar, M; Nguyen, Chinh-Chien; Vu, Manh-Hiep; Do, Trong-On

2018-03-09

The photoassisted catalytic reaction, conventionally known as photocatalysis, is expanding into the field of energy and environmental applications. It is widely known that the discovery of TiO 2 -assisted photochemical reactions has led to several unique applications, such as degradation of pollutants in water and air, hydrogen production through water splitting, fuel conversion, cancer treatment, antibacterial activity, self-cleaning glasses, and concrete. These multifaceted applications of this phenomenon can be enriched and expanded further if this process is equipped with more tools and functions. The term "photoassisted" catalytic reactions clearly emphasizes that photons are required to activate the catalyst; this can be transcended even into the dark if electrons are stored in the material for the later use to continue the catalytic reactions in the absence of light. This can be achieved by equipping the photocatalyst with an electron-storage material to overcome current limitations in photoassisted catalytic reactions. In this context, this article sheds lights on the materials and mechanisms of photocatalytic reactions under light and dark conditions. The manifestation of such systems could be an unparalleled technology in the near future that could influence all spheres of the catalytic sciences. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The redox-Mannich reaction.

PubMed

Chen, Weijie; Seidel, Daniel

2014-06-06

A complement to the classic three-component Mannich reaction, the redox-Mannich reaction, utilizes the same starting materials but incorporates an isomerization step that enables the facile preparation of ring-substituted β-amino ketones. Reactions occur under relatively mild conditions and are facilitated by benzoic acid.

Population dynamics, information transfer, and spatial organization in a chemical reaction network under spatial confinement and crowding conditions

DOE PAGES

Bellesia, Giovanni; Bales, Benjamin B.

2016-10-10

Here, we investigate, via Brownian dynamics simulations, the reaction dynamics of a generic, nonlinear chemical network under spatial confinement and crowding conditions. In detail, the Willamowski-Rossler chemical reaction system has been “extended” and considered as a prototype reaction-diffusion system. These results are potentially relevant to a number of open problems in biophysics and biochemistry, such as the synthesis of primitive cellular units (protocells) and the definition of their role in the chemical origin of life and the characterization of vesicle-mediated drug delivery processes. More generally, the computational approach presented in this work makes the case for the use of spatialmore » stochastic simulation methods for the study of biochemical networks in vivo where the “well-mixed” approximation is invalid and both thermal and intrinsic fluctuations linked to the possible presence of molecular species in low number copies cannot be averaged out.« less

CO2 hydrogenation to methanol on supported Au catalysts under moderate reaction conditions: support and particle size effects.

PubMed

Hartadi, Yeusy; Widmann, Daniel; Behm, R Jürgen

2015-02-01

The potential of metal oxide supported Au catalysts for the formation of methanol from CO2 and H2 under conditions favorable for decentralized and local conversion, which could be concepts for chemical energy storage, was investigated. Significant differences in the catalytic activity and selectivity of Au/Al2 O3 , Au/TiO2 , AuZnO, and Au/ZrO2 catalysts for methanol formation under moderate reaction conditions at a pressure of 5 bar and temperatures between 220 and 240 °C demonstrate pronounced support effects. A high selectivity (>50 %) for methanol formation was obtained only for Au/ZnO. Furthermore, measurements on Au/ZnO samples with different Au particle sizes reveal distinct Au particle size effects: although the activity increases strongly with the decreasing particle size, the selectivity decreases. The consequences of these findings for the reaction mechanism and for the potential of Au/ZnO catalysts for chemical energy storage and a "green" methanol technology are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Acetylation of bacterial cellulose catalyzed by citric acid: Use of reaction conditions for tailoring the esterification extent.

PubMed

Ávila Ramírez, Jhon Alejandro; Gómez Hoyos, Catalina; Arroyo, Silvana; Cerrutti, Patricia; Foresti, María Laura

2016-11-20

Bacterial cellulose (BC) nanoribbons were partially acetylated by a simple direct solvent-free route catalyzed by citric acid. The assay of reaction conditions within chosen intervals (i.e. esterification time (0.5-7h), catalyst content (0.08-1.01mmol/mmol AGU), and temperature (90-140°C)), illustrated the flexibility of the methodology proposed, with reaction variables which can be conveniently manipulated to acetylate BC to the required degree of substitution (DS) within the 0.20-0.73 interval. Within this DS interval, characterization results indicated a surface-only process in which acetylated bacterial cellulose with tunable DS, preserved fibrous structure and increased hydrophobicity could be easily obtained. The feasibility of reusing the catalyst/excess acylant in view of potential scale-up was also illustrated. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mathematical model to predict drivers' reaction speeds.

PubMed

Long, Benjamin L; Gillespie, A Isabella; Tanaka, Martin L

2012-02-01

Mental distractions and physical impairments can increase the risk of accidents by affecting a driver's ability to control the vehicle. In this article, we developed a linear mathematical model that can be used to quantitatively predict drivers' performance over a variety of possible driving conditions. Predictions were not limited only to conditions tested, but also included linear combinations of these tests conditions. Two groups of 12 participants were evaluated using a custom drivers' reaction speed testing device to evaluate the effect of cell phone talking, texting, and a fixed knee brace on the components of drivers' reaction speed. Cognitive reaction time was found to increase by 24% for cell phone talking and 74% for texting. The fixed knee brace increased musculoskeletal reaction time by 24%. These experimental data were used to develop a mathematical model to predict reaction speed for an untested condition, talking on a cell phone with a fixed knee brace. The model was verified by comparing the predicted reaction speed to measured experimental values from an independent test. The model predicted full braking time within 3% of the measured value. Although only a few influential conditions were evaluated, we present a general approach that can be expanded to include other types of distractions, impairments, and environmental conditions.

Synthesis of branched cores by poly-O-alkylation reaction under phase transfer conditions. A systematic study

NASA Astrophysics Data System (ADS)

Landeros, José M.; Silvestre, Hugo A.; Guadarrama, Patricia

2013-04-01

In the present paper is described a systematic study of poly-O-alkylation reactions of pentaerythritol (PE) and 1,1,1-tris(hydroxymethyl)ethane (TME) by 1,4 Michael addition, under phase transfer catalysis (PTC), considering the effect of: (1) the organophilicity of PTC (three different catalysts were tested), (2) PTC concentration (from catalytic to equimolar conditions), and (3) the regime of addition of reactants coexisting in the aqueous phase of the heterogeneous reaction system. The less organophilic transfer agent showed the best performance on these reactions. In our case, benzyltriethylammonium chloride (TEBAC) gathers the best features. The presence of NaOH as base, promotes the interfacial mechanism and not the bulk one. Out of the optimal range of concentration of NaOH (35-40%), competition between nucleophiles can occur, due to the saturation of the medium. Regarding the regime of addition of reactants, the scenario where NaOH and TEBAC are less time in contact, favors the formation of the desired products. Finally, the deprotection of tert-butyl groups of the poly-O-alkylated compounds is described, to get branched cores with terminal carboxylic acid groups in good yields (90-94%). Spectroscopic properties, such as IR, 1H and 13C NMR, of the synthesized compounds are also described.

Mechanistic Study on Cu(II)-Catalyzed Oxidative Cross-Coupling Reaction between Arenes and Boronic Acids under Aerobic Conditions.

PubMed

Zhang, Qian; Liu, Yang; Wang, Ting; Zhang, Xinhao; Long, Chao; Wu, Yun-Dong; Wang, Mei-Xiang

2018-04-25

Substantial attention has been given to modern organocopper chemistry in recent years since copper salts are naturally abundant, cheap, and less toxic in comparison to precious metals. Copper salts also exhibit versatility in catalyzing and mediating carbon-carbon and carbon-heteroatom bond forming reactions. Despite the wide applications of copper salts in catalysis, reaction mechanisms have remained elusive. Using azacalix[1]arene[3]pyridine, an arene-embedded macrocycle, and its isolated and structurally well-defined ArCu(II) and ArCu(III) compounds as molecular tools, we now report an in-depth experimental and computational study on the mechanism of a Cu(II)-catalyzed oxidative cross-coupling reaction between arenes and boronic acids with air as the oxidant. Stoichiometric reaction of organocopper compounds with p-tolylboronic acid validated arylcopper(II) rather than arylcopper(III) as a reactive organometallic intermediate. XPS, EPR, 1 H NMR, HRMS, and UV-vis spectroscopic evidence along with the isolation and quantification of all products and copper speciation, combined with computational analysis of the electronic structure and energetics of the transient intermediates, suggested a reaction sequence involving electrophilic metalation of arene by Cu(II), transmetalation of arylboronate to ArCu(II), the redox reaction between the resulting ArCu(II)Ar' and ArCu(II) to form respectively ArCu(III)Ar' and ArCu(I), and finally reductive elimination of ArCu(III)Ar'. Under aerobic catalytic conditions, all Cu(I) ions released from reductive elimination of ArCu(III)Ar' and from protolysis of ArCu(I) were oxidized by oxygen to regenerate Cu(II) species that enters into the next catalytic cycle. The unraveled reactivity of arylcopper(II) compounds and the catalytic cycle would enrich our knowledge of modern organocopper chemistry and provide useful information in the design of copper-catalyzed reactions.

Christmas Light Display

NASA Astrophysics Data System (ADS)

Ross, Arthur; Renfro, Timothy

2012-03-01

The Digital Electronics class at McMurry University created a Christmas light display that toggles the power of different strands of lights, according to what frequencies are played in a song, as an example of an analog to digital circuit. This was accomplished using a BA3830S IC six-band audio filter and six solid-state relays.

Externally controlled pressure and temperature microreactor for in situ x-ray diffraction, visual and spectroscopic reaction investigations under supercritical and subcritical conditions

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

Diefenbacher, Jason; McKelvy, Michael; Chizmeshya, Andrew V.G.

2005-01-01

A microreactor has been developed for in situ, spectroscopic investigations of materials and reaction processes with full external pressure and temperature control from ambient conditions to 400 deg. C and 310 bar. The sample chamber is in direct contact with an external manifold, whereby gases, liquids or fluids can be injected and their activities controlled prior to and under investigation conditions. The microreactor employs high strength, single crystal moissanite windows which allow direct probe beam interaction with a sample to investigate in situ reaction processes and other materials properties. The relatively large volume of the cell, along with full opticalmore » accessibility and external temperature and pressure control, make this reaction cell well suited for experimental investigations involving any combination of gas, fluid, and solid interactions. The microreactor's capabilities are demonstrated through an in situ x-ray diffraction study of the conversion of a meta-serpentine sample to magnesite under high pressure and temperature. Serpentine is one of the mineral candidates for the implementation of mineral carbonation, an intriguing carbon sequestration candidate technology.« less

Externally controlled pressure and temperature microreactor for in situ x-ray diffraction, visual and spectroscopic reaction investigations under supercritical and subcritial conditions

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

Diefenbacher, J.; McKelvy, M.; Chizemeshya, A.V.

2010-07-13

A microreactor has been developed for in situ, spectroscopic investigations of materials and reaction processes with full external pressure and temperature control from ambient conditions to 400 C and 310 bar. The sample chamber is in direct contact with an external manifold, whereby gases, liquids or fluids can be injected and their activities controlled prior to and under investigation conditions. The microreactor employs high strength, single crystal moissanite windows which allow direct probe beam interaction with a sample to investigate in situ reaction processes and other materials properties. The relatively large volume of the cell, along with full optical accessibilitymore » and external temperature and pressure control, make this reaction cell well suited for experimental investigations involving any combination of gas, fluid, and solid interactions. The microreactor's capabilities are demonstrated through an in situ x-ray diffraction study of the conversion of a meta-serpentine sample to magnesite under high pressure and temperature. Serpentine is one of the mineral candidates for the implementation of mineral carbonation, an intriguing carbon sequestration candidate technology.« less

Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles

NASA Technical Reports Server (NTRS)

Liechty, Derek S.; Lewis, Mark J.

2010-01-01

Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.

Influence of the reaction conditions on the enzyme catalyzed transesterification of castor oil: A possible step in biodiesel production.

PubMed

Andrade, Thalles A; Errico, Massimiliano; Christensen, Knud V

2017-11-01

The identification of the influence of the reaction parameters is of paramount importance when defining a process design. In this work, non-edible castor oil was reacted with methanol to produce a possible component for biodiesel blends, using liquid enzymes as the catalyst. Temperature, alcohol-to-oil molar ratio, enzyme and added water contents were the reaction parameters evaluated in the transesterification reactions. The optimal conditions, giving the optimal final FAME yield and FFA content in the methyl ester-phase was identified. At 35°C, 6.0 methanol-to-oil molar ratio, 5wt% of enzyme and 5wt% of water contents, 94% of FAME yield and 6.1% of FFA in the final composition were obtained. The investigation was completed with the analysis of the component profiles, showing that at least 8h are necessary to reach a satisfactory FAME yield together with a minor FFA content. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sequential Injection Analysis for Optimization of Molecular Biology Reactions

PubMed Central

Allen, Peter B.; Ellington, Andrew D.

2011-01-01

In order to automate the optimization of complex biochemical and molecular biology reactions, we developed a Sequential Injection Analysis (SIA) device and combined this with a Design of Experiment (DOE) algorithm. This combination of hardware and software automatically explores the parameter space of the reaction and provides continuous feedback for optimizing reaction conditions. As an example, we optimized the endonuclease digest of a fluorogenic substrate, and showed that the optimized reaction conditions also applied to the digest of the substrate outside of the device, and to the digest of a plasmid. The sequential technique quickly arrived at optimized reaction conditions with less reagent use than a batch process (such as a fluid handling robot exploring multiple reaction conditions in parallel) would have. The device and method should now be amenable to much more complex molecular biology reactions whose variable spaces are correspondingly larger. PMID:21338059

Optimization of reaction conditions for the electroleaching of manganese from low-grade pyrolusite

NASA Astrophysics Data System (ADS)

Zhang, Xing-ran; Liu, Zuo-hua; Fan, Xing; Lian, Xin; Tao, Chang-yuan

2015-11-01

In the present study, a response surface methodology was used to optimize the electroleaching of Mn from low-grade pyrolusite. Ferrous sulfate heptahydrate was used in this reaction as a reducing agent in sulfuric acid solutions. The effect of six process variables, including the mass ratio of ferrous sulfate heptahydrate to pyrolusite, mass ratio of sulfuric acid to pyrolusite, liquid-to-solid ratio, current density, leaching temperature, and leaching time, as well as their binary interactions, were modeled. The results revealed that the order of these factors with respect to their effects on the leaching efficiency were mass ratio of ferrous sulfate heptahydrate to pyrolusite > leaching time > mass ratio of sulfuric acid to pyrolusite > liquid-to-solid ratio > leaching temperature > current density. The optimum conditions were as follows: 1.10:1 mass ratio of ferrous sulfate heptahydrate to pyrolusite, 0.9:1 mass ratio of sulfuric acid to pyrolusite, liquid-to-solid ratio of 0.7:1, current density of 947 A/m2, leaching time of 180 min, and leaching temperature of 73°C. Under these conditions, the predicted leaching efficiency for Mn was 94.1%; the obtained experimental result was 95.7%, which confirmed the validity of the model.

Controlled release of volatiles under mild reaction conditions: from nature to everyday products.

PubMed

Herrmann, Andreas

2007-01-01

Volatile organic compounds serve in nature as semiochemicals for communication between species, and are often used as flavors and fragrances in our everyday life. The quite limited longevity of olfactive perception has led to the development of pro-perfumes or pro-fragrances--ideally nonvolatile and odorless fragrance precursors which release the active volatiles by bond cleavage. Only a limited amount of reaction conditions, such as hydrolysis, temperature changes, as well as the action of light, oxygen, enzymes, or microorganisms, can be used to liberate the many different chemical functionalities. This Review describes the controlled chemical release of fragrances and discusses additional challenges such as precursor stability during product storage as well as some aspects concerning toxicity and biodegradability. As the same systems can be applied in different areas of research, the scope of this Review covers fragrance delivery as well as the controlled release of volatiles in general.

Reaction Norms in Natural Conditions: How Does Metabolic Performance Respond to Weather Variations in a Small Endotherm Facing Cold Environments?

PubMed Central

Petit, Magali; Vézina, François

2014-01-01

Reaction norms reflect an organisms' capacity to adjust its phenotype to the environment and allows for identifying trait values associated with physiological limits. However, reaction norms of physiological parameters are mostly unknown for endotherms living in natural conditions. Black-capped chickadees (Poecile atricapillus) increase their metabolic performance during winter acclimatization and are thus good model to measure reaction norms in the wild. We repeatedly measured basal (BMR) and summit (Msum) metabolism in chickadees to characterize, for the first time in a free-living endotherm, reaction norms of these parameters across the natural range of weather variation. BMR varied between individuals and was weakly and negatively related to minimal temperature. Msum varied with minimal temperature following a Z-shape curve, increasing linearly between 24°C and −10°C, and changed with absolute humidity following a U-shape relationship. These results suggest that thermal exchanges with the environment have minimal effects on maintenance costs, which may be individual-dependent, while thermogenic capacity is responding to body heat loss. Our results suggest also that BMR and Msum respond to different and likely independent constraints. PMID:25426860

The effect of preparation conditions on the structure and mechanical properties of reaction-sintered silicon nitride

NASA Technical Reports Server (NTRS)

Heinrich, J.

1980-01-01

The microstructure of reaction sintered silicon nitride (RSSN) was changed over a wide range by varying the grain density, grain size of the silicon starting powder, nitriding conditions, and by introducing artificial pores. The influence of single microstructural parameters on mechanical properties like room temperature strength, creep behavior, and resistance to thermal shock was investigated. The essential factors influencing these properties were found to be total porosity, pore size distribution, and the fractions of alpha and beta Si3N4. In view of high temperature engineering applications of RSSN, potentials for optimizing the material's properties by controlled processing are discussed.

Analysis of activation energy in Couette-Poiseuille flow of nanofluid in the presence of chemical reaction and convective boundary conditions

NASA Astrophysics Data System (ADS)

Zeeshan, A.; Shehzad, N.; Ellahi, R.

2018-03-01

The motivation of the current article is to explore the energy activation in MHD radiative Couette-Poiseuille flow nanofluid in horizontal channel with convective boundary conditions. The mathematical model of Buongiorno [1] effectively describes the current flow analysis. Additionally, the impact of chemical reaction is also taken in account. The governing flow equations are simplified with the help of boundary layer approximations. Non-linear coupled equations for momentum, energy and mass transfer are tackled with analytical (HAM) technique. The influence of dimensionless convergence parameter like Brownian motion parameter, radiation parameter, buoyancy ratio parameter, dimensionless activation energy, thermophoresis parameter, temperature difference parameter, dimensionless reaction rate, Schmidt number, Brinkman number, Biot number and convection diffusion parameter on velocity, temperature and concentration profiles are discussed graphically and in tabular form. From the results, it is elaborate that the nanoparticle concentration is directly proportional to the chemical reaction with activation energy and the performance of Brownian motion on nanoparticle concentration gives reverse pattern to that of thermophoresis parameter.

CATALYST-FREE REACTIONS UNDER SOLVENT-FEE CONDITIONS: MICROWAVE-ASSISTED SYNTHESIS OF HETEROCYCLIC HYDRAZONES BELOW THE MELTING POINT OF NEAT REACTANTS: JOURNAL ARTICLE

EPA Science Inventory

NRMRL-CIN-1437 Jeselnik, M., Varma*, R.S., Polanc, S., and Kocevar, M. Catalyst-free Reactions under Solvent-fee Conditions: Microwave-assisted Synthesis of Heterocyclic Hydrazones below the Melting Point of Neat Reactants. Published in: Chemical Communications 18:1716-1717 (200...

[Delayed reactions of active avoidance in white rats under conditions of an alternative choice].

PubMed

Ioseliani, T K; Sikharulidze, N I; Kadagishvili, A Ia; Mitashvili, E G

1995-01-01

It was shown that if the rats had been learned and then tested using conventional pain punishment of erroneous choice they were able to solve the problem of alternative choice only in the period of immediate action of conditioned stimuli. If the pain punishment for erroneously chosen compartment had not been applied in animal learning and testing, rats successfully solved the problem of alternative choice even after 5-second delay. Introduction of pain punishment led to the frustration of earlier elaborated delayed avoidance reactions. Analysis of the obtained results allows us to argue that the apparent incapability of white rats for solving the problems of delayed avoidance is caused by simultaneous action of two different mechanisms, i.e., those of the active and passive avoidance rather than short-term memory deficit.

Influence of growth conditions and surface reaction byproducts on GaN grown via metal organic molecular beam epitaxy: Toward an understanding of surface reaction chemistry

NASA Astrophysics Data System (ADS)

Pritchett, David; Henderson, Walter; Burnham, Shawn D.; Doolittle, W. Alan

2006-04-01

The surface reaction byproducts during the growth of GaN films via metal organic molecular beam epitaxy (MOMBE) were investigated as a means to optimize material properties. Ethylene and ethane were identified as the dominant surface reaction hydrocarbon byproducts, averaging 27.63% and 7.15% of the total gas content present during growth. Intense ultraviolet (UV) photoexcitation during growth was found to significantly increase the abundance of ethylene and ethane while reducing the presence of H2 and N2. At 920°C, UV excitation was shown to enhance growth rate and crystalline quality while reducing carbon incorporation. Over a limited growth condition range, a 4.5×1019-3.4×1020 cm-3 variation in carbon incorporation was achieved at constant high vacuum. Coupled with growth rate gains, UV excitation yielded films with ˜58% less integrated carbon content. Structural material property variations are reported for various ammonia flows and growth temperatures. The results suggest that high carbon incorporation can be achieved and regulated during MOMBE growth and that in-situ optimization through hydrocarbon analysis may provide further enhancement in the allowable carbon concentration range.

Designing flexible instructional space for teaching introductory physics with emphasis on inquiry and collaborative active learning

NASA Astrophysics Data System (ADS)

Bykov, Tikhon

2010-03-01

In recent years McMurry University's introductory physics curriculum has gone through a series of significant changes to achieve better integration of traditional course components (lecture/lab/discussion) by means of instructional design and technology. A system of flexible curriculum modules with emphasis on inquiry-based teaching and collaborative active learning has been introduced. To unify module elements, a technology suite has been used that consists of Tablet PC's and software applications including Physlets, tablet-adapted personal response system, PASCO data acquisition systems, and MS One-note collaborative writing software. Adoption of the new teaching model resulted in reevaluation of existing instructional spaces. The new teaching space will be created during the renovation of the McMurry Science Building. This space will allow for easy transitions between lecture and laboratory modes. Movable partitions will be used to accommodate student groups of different sizes. The space will be supportive of small peer-group activities with easy-to-reconfigure furniture, multiple white and black board surfaces and multiple projection screens. The new space will be highly flexible to account for different teaching functions, different teaching modes and learning styles.

The Aldol Addition and Condensation: The Effect of Conditions on Reaction Pathway

ERIC Educational Resources Information Center

Crouch, R. David; Richardson, Amie; Howard, Jessica L.; Harker, Rebecca L.; Barker, Kathryn H.

2007-01-01

The reaction of a ketone and an aldehyde in aqueous Na[subscript 2]CO[subscript 2] is described. This experiment is performed in the absence of strong bases or organic solvents and offers the opportunity for students to observe the critical role that reaction temperature and base strength have in determining the product of the base-mediated…

Direct Monte Carlo simulation of chemical reaction systems: Simple bimolecular reactions

NASA Astrophysics Data System (ADS)

Piersall, Shannon D.; Anderson, James B.

1991-07-01

In applications to several simple reaction systems we have explored a ``direct simulation'' method for predicting and understanding the behavior of gas phase chemical reaction systems. This Monte Carlo method, originated by Bird, has been found remarkably successful in treating a number of difficult problems in rarefied dynamics. Extension to chemical reactions offers a powerful tool for treating reaction systems with nonthermal distributions, with coupled gas-dynamic and reaction effects, with emission and adsorption of radiation, and with many other effects difficult to treat in any other way. The usual differential equations of chemical kinetics are eliminated. For a bimolecular reaction of the type A+B→C+D with a rate sufficiently low to allow a continued thermal equilibrium of reactants we find that direct simulation reproduces the expected second order kinetics. Simulations for a range of temperatures yield the activation energies expected for the reaction models specified. For faster reactions under conditions leading to a depletion of energetic reactant species, the expected slowing of reaction rates and departures from equilibrium distributions are observed. The minimum sample sizes required for adequate simulations are as low as 1000 molecules for these cases. The calculations are found to be simple and straightforward for the homogeneous systems considered. Although computation requirements may be excessively high for very slow reactions, they are reasonably low for fast reactions, for which nonequilibrium effects are most important.

Explore the reaction mechanism of the Maillard reaction: a density functional theory study.

PubMed

Ren, Ge-Rui; Zhao, Li-Jiang; Sun, Qiang; Xie, Hu-Jun; Lei, Qun-Fang; Fang, Wen-Jun

2015-05-01

The mechanism of Maillard reaction has been investigated by means of density functional theory calculations in the gaseous phase and aqueous solution. The Maillard reaction is a cascade of consecutive and parallel reaction. In the present model system study, glucose and glycine were taken as the initial reactants. On the basis of previous experimental results, the mechanisms of Maillard reaction have been proposed, and the possibility for the formation of different compounds have been evaluated through calculating the relative energy changes for different steps of reaction under different pH conditions. Our calculations reveal that the TS3 in Amadori rearrangement reaction is the rate-determining step of Maillard reaction with the activation barriers of about 66.7 and 68.8 kcal mol(-1) in the gaseous phase and aqueous solution, respectively. The calculation results are in good agreement with previous studies and could provide insights into the reaction mechanism of Maillard reaction, since experimental evaluation of the role of intermediates in the Maillard reaction is quite complicated.

Benzene Adsorption - A Significant Inhibitor for the Hydrogen Oxidation Reaction in Alkaline Conditions

DOE PAGES

Gonzales, Ivana; Chung, Hoon Taek; Kim, Yu Seung

2017-09-25

Slow hydrogen oxidation reaction (HOR) kinetics on Pt under alkaline conditions is a significant technical barrier for the development of high-performance hydroxide exchange membrane fuel cells. Here we report that benzene adsorption on Pt is a major factor responsible for the sluggish HOR. Furthermore, we demonstrate that bimetallic catalysts, such as PtMo/C, PtNi/C, and PtRu/C, can reduce the adsorption of benzene and thereby improve HOR activity. In particular, the HOR voltammogram of PtRu/C in 0.1 M benzyl ammonium showed minimal benzene adsorption. Density functional theory calculations indicate that the adsorption of benzyl ammonium on the bimetallic PtRu is endergonic formore » all four possible orientations of the cation, which explains the significantly better HOR activity observed for the bimetallic catalysts. In conclusion, the new HOR inhibition mechanism described here provides insights for the design of future polymer electrolytes and electrocatalysts for better-performing polymer membrane-based fuel cells.« less

Role of choline and glycine betaine in the formation of N,N-dimethylpiperidinium (mepiquat) under Maillard reaction conditions.

PubMed

Bessaire, Thomas; Tarres, Adrienne; Stadler, Richard H; Delatour, Thierry

2014-01-01

This study is the first to examine the role of choline and glycine betaine, naturally present in some foods, in particular in cereal grains, to generate N,N-dimethylpiperidinium (mepiquat) under Maillard conditions via transmethylation reactions involving the nucleophile piperidine. The formation of mepiquat and its intermediates piperidine - formed by cyclisation of free lysine in the presence of reducing sugars - and N-methylpiperidine were monitored over time (240°C, up to 180 min) using high-resolution mass spectrometry in a model system comprised of a ternary mixture of lysine/fructose/alkylating agent (choline or betaine). The reaction yield was compared with data recently determined for trigonelline, a known methylation agent present naturally in coffee beans. The role of choline and glycine betaine in nucleophilic displacement reactions was further supported by experiments carried out with stable isotope-labelled precursors (¹³C- and deuterium-labelled). The results unequivocally demonstrated that the piperidine ring of mepiquat originates from the carbon chain of lysine, and that either choline or glycine betaine furnishes the N-methyl groups. The kinetics of formation of the corresponding demethylated products of both choline and glycine betaine, N,N-demethyl-2-aminoethanol and N,N-dimethylglycine, respectively, were also determined using high-resolution mass spectrometry.

Reaction rates for mesoscopic reaction-diffusion kinetics

DOE PAGES

Hellander, Stefan; Hellander, Andreas; Petzold, Linda

2015-02-23

The mesoscopic reaction-diffusion master equation (RDME) is a popular modeling framework frequently applied to stochastic reaction-diffusion kinetics in systems biology. The RDME is derived from assumptions about the underlying physical properties of the system, and it may produce unphysical results for models where those assumptions fail. In that case, other more comprehensive models are better suited, such as hard-sphere Brownian dynamics (BD). Although the RDME is a model in its own right, and not inferred from any specific microscale model, it proves useful to attempt to approximate a microscale model by a specific choice of mesoscopic reaction rates. In thismore » paper we derive mesoscopic scale-dependent reaction rates by matching certain statistics of the RDME solution to statistics of the solution of a widely used microscopic BD model: the Smoluchowski model with a Robin boundary condition at the reaction radius of two molecules. We also establish fundamental limits on the range of mesh resolutions for which this approach yields accurate results and show both theoretically and in numerical examples that as we approach the lower fundamental limit, the mesoscopic dynamics approach the microscopic dynamics. Finally, we show that for mesh sizes below the fundamental lower limit, results are less accurate. Thus, the lower limit determines the mesh size for which we obtain the most accurate results.« less

Reaction rates for mesoscopic reaction-diffusion kinetics

PubMed Central

Hellander, Stefan; Hellander, Andreas; Petzold, Linda

2016-01-01

The mesoscopic reaction-diffusion master equation (RDME) is a popular modeling framework frequently applied to stochastic reaction-diffusion kinetics in systems biology. The RDME is derived from assumptions about the underlying physical properties of the system, and it may produce unphysical results for models where those assumptions fail. In that case, other more comprehensive models are better suited, such as hard-sphere Brownian dynamics (BD). Although the RDME is a model in its own right, and not inferred from any specific microscale model, it proves useful to attempt to approximate a microscale model by a specific choice of mesoscopic reaction rates. In this paper we derive mesoscopic scale-dependent reaction rates by matching certain statistics of the RDME solution to statistics of the solution of a widely used microscopic BD model: the Smoluchowski model with a Robin boundary condition at the reaction radius of two molecules. We also establish fundamental limits on the range of mesh resolutions for which this approach yields accurate results and show both theoretically and in numerical examples that as we approach the lower fundamental limit, the mesoscopic dynamics approach the microscopic dynamics. We show that for mesh sizes below the fundamental lower limit, results are less accurate. Thus, the lower limit determines the mesh size for which we obtain the most accurate results. PMID:25768640

Nonequilibrium thermodynamics and a fluctuation theorem for individual reaction steps in a chemical reaction network

NASA Astrophysics Data System (ADS)

Pal, Krishnendu; Das, Biswajit; Banerjee, Kinshuk; Gangopadhyay, Gautam

2015-09-01

We have introduced an approach to nonequilibrium thermodynamics of an open chemical reaction network in terms of the propensities of the individual elementary reactions and the corresponding reverse reactions. The method is a microscopic formulation of the dissipation function in terms of the relative entropy or Kullback-Leibler distance which is based on the analogy of phase space trajectory with the path of elementary reactions in a network of chemical process. We have introduced here a fluctuation theorem valid for each opposite pair of elementary reactions which is useful in determining the contribution of each sub-reaction on the nonequilibrium thermodynamics of overall reaction. The methodology is applied to an oligomeric enzyme kinetics at a chemiostatic condition that leads the reaction to a nonequilibrium steady state for which we have estimated how each step of the reaction is energy driven or entropy driven to contribute to the overall reaction.

Biodiesel production from various oils under supercritical fluid conditions by Candida antartica lipase B using a stepwise reaction method.

PubMed

Lee, Jong Ho; Kwon, Cheong Hoon; Kang, Jeong Won; Park, Chulhwan; Tae, Bumseok; Kim, Seung Wook

2009-05-01

In this study, we evaluate the effects of various reaction factors, including pressure, temperature, agitation speed, enzyme concentration, and water content to increase biodiesel production. In addition, biodiesel was produced from various oils to establish the optimal enzymatic process of biodiesel production. Optimal conditions were determined to be as follows: pressure 130 bar, temperature 45 degrees C, agitation speed 200 rpm, enzyme concentration 20%, and water contents 10%. Among the various oils used for production, olive oil showed the highest yield (65.18%) upon transesterification. However, when biodiesel was produced using a batch system, biodiesel conversion yield was not increased over 65%; therefore, a stepwise reaction was conducted to increase biodiesel production. When a reaction medium with an initial concentration of methanol of 60 mmol was used and adjusted to maintain this concentration of methanol every 1.5 h during biodiesel production, the conversion yield of biodiesel was 98.92% at 6 h. Finally, reusability was evaluated using immobilized lipase to determine if this method was applicable for industrial biodiesel production. When biodiesel was produced repeatedly, the conversion rate was maintained at over 85% after eight reuses.

Reaction pathways towards the formation of dolomite-analogues at ambient conditions

NASA Astrophysics Data System (ADS)

Pimentel, Carlos; Pina, Carlos M.

2016-04-01

In this paper we present results of a study of the crystallisation behaviour of the dolomite-analogues norsethite and PbMg(CO3)2 at room temperature and atmospheric pressure. Whereas precipitation of norsethite was previously obtained by mixing solutions (Hood et al., 1974; Pimentel and Pina, 2014a,b), we report, for the first time, the synthesis of PbMg(CO3)2 by using the same method. The formation of both phases was promoted by ageing slurries for periods of time ranging from a few days (norsethite) up to 6 months (PbMg(CO3)2). The crystallisation of both norsethite and PbMg(CO3)2 occurs by sequences of dissolution-precipitation reactions involving several amorphous and crystalline precursor phases, which were identified and characterised by X-ray diffraction and scanning electron microscopy. Depending on the initial composition and Ba:Mg and Pb:Mg ratios in the slurries, different precursors and reaction kinetics were observed. This demonstrates the existence of different reaction pathways towards the formation of the investigated dolomite-analogues. Our experimental results provide new insights into the possible mechanisms of formation of dolomite and other double carbonates in nature.

Discussion of the Investigation Method on the Reaction Kinetics of Metallurgical Reaction Engineering

NASA Astrophysics Data System (ADS)

Du, Ruiling; Wu, Keng; Zhang, Jiazhi; Zhao, Yong

Reaction kinetics of metallurgical physical chemistry which was successfully applied in metallurgy (as ferrous metallurgy, non-ferrous metallurgy) became an important theoretical foundation for subject system of traditional metallurgy. Not only the research methods were very perfect, but also the independent structures and systems of it had been formed. One of the important tasks of metallurgical reaction engineering was the simulation of metallurgical process. And then, the mechanism of reaction process and the conversion time points of different control links should be obtained accurately. Therefore, the research methods and results of reaction kinetics in metallurgical physical chemistry were not very suitable for metallurgical reaction engineering. In order to provide the definite conditions of transmission, reaction kinetics parameters and the conversion time points of different control links for solving the transmission and reaction equations in metallurgical reaction engineering, a new method for researching kinetics mechanisms in metallurgical reaction engineering was proposed, which was named stepwise attempt method. Then the comparison of results between the two methods and the further development of stepwise attempt method were discussed in this paper. As a new research method for reaction kinetics in metallurgical reaction engineering, stepwise attempt method could not only satisfy the development of metallurgical reaction engineering, but also provide necessary guarantees for establishing its independent subject system.

Multichannel quench-flow microreactor chip for parallel reaction monitoring.

PubMed

Bula, Wojciech P; Verboom, Willem; Reinhoudt, David N; Gardeniers, Han J G E

2007-12-01

This paper describes a multichannel silicon-glass microreactor which has been utilized to investigate the kinetics of a Knoevenagel condensation reaction under different reaction conditions. The reaction is performed on the chip in four parallel channels under identical conditions but with different residence times. A special topology of the reaction coils overcomes the common problem arising from the difference in pressure drop of parallel channels having different length. The parallelization of reaction coils combined with chemical quenching at specific locations results in a considerable reduction in experimental effort and cost. The system was tested and showed good reproducibility in flow properties and reaction kinetic data generation.

Diffusion and reactivity of ground-state nitrogen atoms N(4S) between 3 and 15 K: application to the hydrogen abstraction reaction from methane under non-energetic conditions

NASA Astrophysics Data System (ADS)

Nourry, Sendres; Krim, Lahouari

2015-07-01

We have characterized the CH4 + N(4S) reaction in solid phase, at very low temperature, under non-energetic conditions and where the CH4 and N reactants are in their ground states. A microwave-driven atomic source has been used to generate ground-state nitrogen atoms N(4S), and experiments have been carried out at temperatures as low as 3 K to reduce the mobility of the trapped species in solid phase and hence to freeze the first step of the CH4 + N reaction pathway. Leaving the formed solid sample in the dark for a while allows all trapped reactants to relax to the ground state, specifically radicals and excited species streaming from the plasma discharge. Such a method could be the only possibility of proving that the CH4 + N reaction occurs between CH4 and N reactants in their ground states without any additional energy to initiate the chemical process. The appearance of the CH3 reaction product, just by inducing the mobility of N atoms between 3 and 11 K, translates that a hydrogen abstraction reaction from methane, under non-energetic conditions, will start occurring at very low temperature. The formation of methyl radical, under these experimental conditions, is due to recombination processes N(4S)-N(4S) of ground-state nitrogen atoms without any contribution of cosmic ray particles or high-energy photons.

An Analysis of the Algebraic Method for Balancing Chemical Reactions.

ERIC Educational Resources Information Center

Olson, John A.

1997-01-01

Analyzes the algebraic method for balancing chemical reactions. Introduces a third general condition that involves a balance between the total amount of oxidation and reduction. Requires the specification of oxidation states for all elements throughout the reaction. Describes the general conditions, the mathematical treatment, redox reactions, and…

"Greening up" the Suzuki Reaction

ERIC Educational Resources Information Center

Aktoudianakis, Evangelos; Chan, Elton; Edward, Amanda R.; Jarosz, Isabel; Lee, Vicki; Mui, Leo; Thatipamala, Sonya S.; Dicks, Andrew P.

2008-01-01

This article describes the rapid, green synthesis of a biaryl compound (4-phenylphenol) via a Pd(0)-catalyzed Suzuki cross-coupling reaction in water. Mild reaction conditions and operational simplicity makes this experiment especially amenable to both mid- and upper-level undergraduates. The methodology exposes students to purely aqueous…

Physiological reactions of a passenger to transportation conditions

NASA Technical Reports Server (NTRS)

Lakshin, A. M.; Novoselov, V. P.

1980-01-01

The effect of transportation conditions on the performance capacity of a passenger were studied, in order to establish the time for his most rapid inclusion in production activity after the trip. It was concluded that the transportation conditions impair the functional condition of the passenger's organism. The restoration of the functional state to the initial level occurs mainly in the space of one day. It is shown that it is necessary to take into consideration the adaptation of the organism during transfer to another climate zone.

Real-Time Optical Monitoring of Flow Kinetics and Gas Phase Reactions Under High-Pressure OMCVD Conditions

NASA Technical Reports Server (NTRS)

Dietz, N.; McCall, S.; Bachmann, K. J.

2001-01-01

This contribution addresses the real-time optical characterization of gas flow and gas phase reactions as they play a crucial role for chemical vapor phase depositions utilizing elevated and high pressure chemical vapor deposition (HPCVD) conditions. The objectives of these experiments are to validate on the basis of results on real-time optical diagnostics process models simulation codes, and provide input parameter sets needed for analysis and control of chemical vapor deposition at elevated pressures. Access to microgravity is required to retain high pressure conditions of laminar flow, which is essential for successful acquisition and interpretation of the optical data. In this contribution, we describe the design and construction of the HPCVD system, which include access ports for various optical methods of real-time process monitoring and to analyze the initial stages of heteroepitaxy and steady-state growth in the different pressure ranges. To analyze the onset of turbulence, provisions are made for implementation of experimental methods for in-situ characterization of the nature of flow. This knowledge will be the basis for the design definition of experiments under microgravity, where gas flow conditions, gas phase and surface chemistry, might be analyzed by remote controlled real-time diagnostics tools, developed in this research project.

Unraveling reaction pathways and specifying reaction kinetics for complex systems.

PubMed

Vinu, R; Broadbelt, Linda J

2012-01-01

Many natural and industrial processes involve a complex set of competing reactions that include several different species. Detailed kinetic modeling of such systems can shed light on the important pathways involved in various transformations and therefore can be used to optimize the process conditions for the desired product composition and properties. This review focuses on elucidating the various components involved in modeling the kinetics of pyrolysis and oxidation of polymers. The elementary free radical steps that constitute the chain reaction mechanism of gas-phase/nonpolar liquid-phase processes are outlined. Specification of the rate coefficients of the various reaction families, which is central to the theme of kinetics, is described. Construction of the reaction network on the basis of the types of end groups and reactive moieties in a polymer chain is discussed. Modeling frameworks based on the method of moments and kinetic Monte Carlo are evaluated using illustrations. Finally, the prospects and challenges in modeling biomass conversion are addressed.

Chemoselective O-acylation of hydroxyamino acids and amino alcohols under acidic reaction conditions: History, scope and applications

PubMed Central

2015-01-01

Summary Amino acids, whether natural, semisynthetic or synthetic, are among the most important and useful chiral building blocks available for organic chemical synthesis. In principle, they can function as inexpensive, chiral and densely functionalized starting materials. On the other hand, the use of amino acid starting materials routinely necessitates protective group chemistry, and in reality, large-scale preparations of even the simplest side-chain derivatives of many amino acids often become annoyingly strenuous due to the necessity of employing protecting groups, on one or more of the amino acid functionalities, during the synthetic sequence. However, in the case of hydroxyamino acids such as hydroxyproline, serine, threonine, tyrosine and 3,4-dihydroxyphenylalanine (DOPA), many O-acyl side-chain derivatives are directly accessible via a particularly expedient and scalable method not commonly applied until recently. Direct acylation of unprotected hydroxyamino acids with acyl halides or carboxylic anhydrides under appropriately acidic reaction conditions renders possible chemoselective O-acylation, furnishing the corresponding side-chain esters directly, on multigram-scale, in a single step, and without chromatographic purification. Assuming a certain degree of stability under acidic reaction conditions, the method is also applicable for a number of related compounds, such as various amino alcohols and the thiol-functional amino acid cysteine. While the basic methodology underlying this approach has been known for decades, it has evolved through recent developments connected to amino acid-derived chiral organocatalysts to become a more widely recognized procedure for large-scale preparation of many useful side-chain derivatives of hydroxyamino acids and related compounds. Such derivatives are useful in peptide chemistry and drug development, as amino acid amphiphiles for asymmetric catalysis, and as amino acid acrylic precursors for preparation of

DATA COLLECTION CONSTRAINTS FOR THE USE OF LENGTH HETEROGENEITY POLYMERASE CHAIN REACTION (LH-PCR) AS AN INDICATOR OF STREAM SANITARY AND ECOLOGICAL CONDITION

EPA Science Inventory

This study is part of a larger project for the development of bacterial indicators of stream sanitary and ecological condition. Here we report preliminary research on the use of Length Heterogeneity Polymerase Chain Reaction (LH-PCR), which discriminates among 16S rRNA genes bas...

Toward an Interpersonal Paradigm for Superior-Subordinate Communication.

DTIC Science & Technology

1983-11-01

Super- vision in a Large Industrial Organization." Disserta- tion Abstracts International, 34 (1974), 4460A (Kent State). Farace , Richard V.; Peter R...see, among others, Haney, 1976; Farace , Monge, and Russell, 1977; Mitchell, 1970; McMurry, n.d.; Harriman, 1974), and a problem for which no dearth of...for subordinates a positive 31 correlation exists between trust and their supervisors’ per- ceived willingness to listen. Farace , Monge, and Russell

Adaptive locomotor training on an end-effector gait robot: evaluation of the ground reaction forces in different training conditions.

PubMed

Tomelleri, Christopher; Waldner, Andreas; Werner, Cordula; Hesse, Stefan

2011-01-01

The main goal of robotic gait rehabilitation is the restoration of independent gait. To achieve this goal different and specific patterns have to be practiced intensively in order to stimulate the learning process of the central nervous system. The gait robot G-EO Systems was designed to allow the repetitive practice of floor walking, stair climbing and stair descending. A novel control strategy allows training in adaptive mode. The force interactions between the foot and the ground were analyzed on 8 healthy volunteers in three different conditions: real floor walking on a treadmill, floor walking on the gait robot in passive mode, floor walking on the gait robot in adaptive mode. The ground reaction forces were measured by a Computer Dyno Graphy (CDG) analysis system. The results show different intensities of the ground reaction force across all of the three conditions. The intensities of force interactions during the adaptive training mode are comparable to the real walking on the treadmill. Slight deviations still occur in regard to the timing pattern of the forces. The adaptive control strategy comes closer to the physiological swing phase than the passive mode and seems to be a promising option for the treatment of gait disorders. Clinical trials will validate the efficacy of this new option in locomotor therapy on the patients. © 2011 IEEE

Effects of reaction conditions on the emission behaviors of arsenic, cadmium and lead during sewage sludge pyrolysis.

PubMed

Han, Hengda; Hu, Song; Syed-Hassan, Syed Shatir A; Xiao, Yiming; Wang, Yi; Xu, Jun; Jiang, Long; Su, Sheng; Xiang, Jun

2017-07-01

Sewage sludge is an important class of bioresources whose energy content could be exploited using pyrolysis technology. However, some harmful trace elements in sewage sludge can escape easily to the gas phase during pyrolysis, increasing the potential of carcinogenic material emissions to the atmosphere. This study investigates emission characteristics of arsenic, cadmium and lead under different pyrolysis conditions for three different sewage sludge samples. The increased temperature (within 723-1123K) significantly promoted the cadmium and lead emissions, but its influence on arsenic emission was not pronounced. The releasing rate order of the three trace elements is volatile arsenic compounds>cadmium>lead in the beginning of pyrolysis. Fast heating rates promoted the emission of trace elements for the sludge containing the highest amount of ash, but exhibited an opposite effect for other studied samples. Overall, the high ash sludge released the least trace elements almost under all reaction conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Highly efficient electrochemical ammonia synthesis via nitrogen reduction reactions on a VN nanowire array under ambient conditions.

PubMed

Zhang, Xiaoping; Kong, Rong-Mei; Du, Huitong; Xia, Lian; Qu, Fengli

2018-05-22

The development of a sustainable route to ammonia production is one of the most attractive targets in chemistry. The primary method of ammonia production, Haber-Bosch process, can bring about excessive consumption of fossil fuels and large CO2 emission. In this communication, we develop a VN nanowire array on carbon cloth (VN/CC) as a high-performance catalyst for the nitrogen reduction reaction (NRR) under ambient conditions. Such an electrocatalyst achieves high ammonia yield (2.48 × 10-10 mol-1 s-1 cm-2) and faradaic efficiency (3.58%) at -0.3 V versus RHE in 0.1 M HCl, outperforming most reported results for N2 fixation under ambient conditions, and even comparing favorably with those obtained under high temperatures and/or pressures. This work not only provides us an attractive catalyst material for the NRR in acidic media, but would also open up an exciting new avenue to the rational design and fabrication of transition metal nitrides for the NRR.

Knoevenagel Reaction of Unprotected Sugars

NASA Astrophysics Data System (ADS)

Scherrmann, Marie-Christine

The Knoevenagel reaction of unprotected sugars was investigated in the 1950s using zinc chloride as promoter. The so-called Garcia Gonzalez reaction had been almost forgotten for 50 years, until the emergence of new water tolerant catalysts having Lewis acid behavior. The reaction was thus reinvestigated and optimal conditions have been found to prepare trihydroxylated furan derivatives from pentose or β-tetrahydrofuranylfuran from hexoses with non-cyclic β-keto ester or β-diketones. Other valuable compounds such as β-linked tetrahydrobenzofuranyl glycosides or hydroxyalkyl-3,3,6,6,-tetramethyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione can be obtained using cyclic β-dicarbonylic derivatives. Apart from one report in the 1950s, the Knoevenagel reaction of unprotected carbohydrate in basic condition has been studied only in the mid-1980s to prepare C-glycosyl barbiturates from barbituric acids and, later on, from non-cyclic β-diketones, β-C-glycosidic ketones. The efficient method exploited to prepare such compounds has found an industrial development in cosmetics.

Malonic acid concentration as a control parameter in the kinetic analysis of the Belousov-Zhabotinsky reaction under batch conditions.

PubMed

Blagojević, Slavica M; Anić, Slobodan R; Cupić, Zeljko D; Pejić, Natasa D; Kolar-Anić, Ljiljana Z

2008-11-28

The influence of the initial malonic acid concentration [MA]0 (8.00 x 10(-3) < or = [MA]0 < or = 4.30 x 10(-2) mol dm(-3)) in the presence of bromate (6.20 x 10(-2) mol dm(-3)), bromide (1.50 x 10(-5) mol dm(-3)), sulfuric acid (1.00 mol dm(-3)) and cerium sulfate (2.50 x 10(-3) mol dm(-3)) on the dynamics and the kinetics of the Belousov-Zhabotinsky (BZ) reactions was examined under batch conditions at 30.0 degrees C. The kinetics of the BZ reaction was analyzed by the earlier proposed method convenient for the examinations of the oscillatory reactions. In the defined region of parameters where oscillograms with only large-amplitude relaxation oscillations appeared, the pseudo-first order of the overall malonic acid decomposition with a corresponding rate constant of 2.14 x 10(-2) min(-1) was established. The numerical results on the dynamics and kinetics of the BZ reaction, carried out by the known skeleton model including the Br2O species, were in good agreement with the experimental ones. The already found saddle node infinite period (SNIPER) bifurcation point in transition from a stable quasi-steady state to periodic orbits and vice versa is confirmed by both experimental and numerical investigations of the system under consideration. Namely, the large-amplitude relaxation oscillations with increasing periods between oscillations in approaching the bifurcation points at the beginning and the end of the oscillatory domain, together with excitability of the stable quasi-steady states in their vicinity are obtained.

Reactions and properties of clusters

NASA Astrophysics Data System (ADS)

Castleman, A. W., Jr.

1992-09-01

The elucidation from a molecular point of view of the differences and similarities in the properties and reactivity of matter in the gaseous compared to the condensed state is a subject of considerable current interest. One of the promising approaches to this problem is to utilize mass spectrometry in conjunction with laser spectroscopy and fast-flow reaction devices to investigate the changing properties, structure and reactivity of clusters as a function of the degree of solvation under well-controlled conditions. In this regard, an investigation of molecular cluster ions has provided considerable new insight into the basic mechanisms of ion reactions within a cluster, and this paper reviews some of the recent advances in cluster production, the origin of magic numbers and relationship to cluster ion stabilities, and solvation effects on reactions. There have been some notable advances in the production of large cluster ions under thermal reaction conditions, enabling a systematic study of the influence of solvation on reactions to be carried out. These and other new studies of magic numbers have traced their origin to the thermochemical stability of cluster ions. There are several classes of reaction where solvation has a notable influence on reactivity. A particularly interesting example comes from recent studies of the reactions of the hydroxyl anion with CO2 and SO2, studied as a function of the degree of hydration of OH-. Both reactions are highly exothermic, yet the differences in reactivity are dramatic. In the case of SO2, the reaction occurs at near the collision rate. By contrast, CO2 reactivity plummets dramatically for clusters having more than four water molecules. The slow rate is in accord with observations in the liquid phase.

Chemical memory reactions induced bursting dynamics in gene expression.

PubMed

Tian, Tianhai

2013-01-01

Memory is a ubiquitous phenomenon in biological systems in which the present system state is not entirely determined by the current conditions but also depends on the time evolutionary path of the system. Specifically, many memorial phenomena are characterized by chemical memory reactions that may fire under particular system conditions. These conditional chemical reactions contradict to the extant stochastic approaches for modeling chemical kinetics and have increasingly posed significant challenges to mathematical modeling and computer simulation. To tackle the challenge, I proposed a novel theory consisting of the memory chemical master equations and memory stochastic simulation algorithm. A stochastic model for single-gene expression was proposed to illustrate the key function of memory reactions in inducing bursting dynamics of gene expression that has been observed in experiments recently. The importance of memory reactions has been further validated by the stochastic model of the p53-MDM2 core module. Simulations showed that memory reactions is a major mechanism for realizing both sustained oscillations of p53 protein numbers in single cells and damped oscillations over a population of cells. These successful applications of the memory modeling framework suggested that this innovative theory is an effective and powerful tool to study memory process and conditional chemical reactions in a wide range of complex biological systems.

Effects of a Single Water Molecule on the Reaction Barrier of Interstellar CO2 Formation Reaction.

PubMed

Tachikawa, Hiroto; Kawabata, Hiroshi

2016-08-25

The mechanism by which CO2 is formed in the interstellar space remains a mystery. The most likely reaction is collision between CO and OH; however, previous theoretical works have shown that the activation barrier for CO2 formation is high enough to prevent the reaction at the low thermal conditions of space (∼10 K). The effects of single water molecule on the reaction barrier of CO2 formation from reaction between CO and OH have been investigated here by means of ab initio calculation. The barrier height along the lowest-energy pathway in the reaction between CO and OH in the absence of the H2O molecule was calculated to be 2.3 kcal/mol when CCSD(T) energy corrections are combined with the MP2 basis set limit. In the case of the hydrated (H2O-CO-OH) system, the inclusion of a single H2O molecule into the system significantly decreased the barrier height to 0.2 kcal/mol. This suggests that CO2 can be formed when CO and OH react in the presence of H2O, even under thermal conditions as low as 10 K.

Catalytic Organometallic Reactions of Ammonia

PubMed Central

Klinkenberg, Jessica L.

2012-01-01

Until recently, ammonia had rarely succumbed to catalytic transformations with homogeneous catalysts, and the development of such reactions that are selective for the formation of single products under mild conditions has encountered numerous challenges. However, recently developed catalysts have allowed several classes of reactions to create products with nitrogen-containing functional groups from ammonia. These reactions include hydroaminomethylation, reductive amination, alkylation, allylic substitution, hydroamination, and cross-coupling. This Minireview describes examples of these processes and the factors that control catalyst activity and selectivity. PMID:20857466

Reaction chemistry in rechargeable Li-O2 batteries.

PubMed

Lim, Hee-Dae; Lee, Byungju; Bae, Youngjoon; Park, Hyeokjun; Ko, Youngmin; Kim, Haegyeom; Kim, Jinsoo; Kang, Kisuk

2017-05-22

The seemingly simple reaction of Li-O 2 batteries involving lithium and oxygen makes this chemistry attractive for high-energy-density storage systems; however, achieving this reaction in practical rechargeable Li-O 2 batteries has proven difficult. The reaction paths leading to the final Li 2 O 2 discharge products can be greatly affected by the operating conditions or environment, which often results in major side reactions. Recent research findings have begun to reveal how the reaction paths may be affected by the surrounding conditions and to uncover the factors contributing to the difficulty in achieving the reactions of lithium and oxygen. This progress report describes the current state of understanding of the electrode reaction mechanisms in Li-O 2 batteries; the factors that affect reaction pathways; and the effect of cell components such as solvents, salts, additives, and catalysts on the discharge product and its decomposition during charging. This comprehensive review of the recent progress in understanding the reaction chemistry of the Li-O 2 system will serve as guidelines for future research and aid in the development of reliable high-energy-density rechargeable Li-O 2 batteries.

Connecting localized DNA strand displacement reactions

NASA Astrophysics Data System (ADS)

Mullor Ruiz, Ismael; Arbona, Jean-Michel; Lad, Amitkumar; Mendoza, Oscar; Aimé, Jean-Pierre; Elezgaray, Juan

2015-07-01

Logic circuits based on DNA strand displacement reactions have been shown to be versatile enough to compute the square root of four-bit numbers. The implementation of these circuits as a set of bulk reactions faces difficulties which include leaky reactions and intrinsically slow, diffusion-limited reaction rates. In this paper, we consider simple examples of these circuits when they are attached to platforms (DNA origamis). As expected, constraining distances between DNA strands leads to faster reaction rates. However, it also induces side-effects that are not detectable in the solution-phase version of this circuitry. Appropriate design of the system, including protection and asymmetry between input and fuel strands, leads to a reproducible behaviour, at least one order of magnitude faster than the one observed under bulk conditions.Logic circuits based on DNA strand displacement reactions have been shown to be versatile enough to compute the square root of four-bit numbers. The implementation of these circuits as a set of bulk reactions faces difficulties which include leaky reactions and intrinsically slow, diffusion-limited reaction rates. In this paper, we consider simple examples of these circuits when they are attached to platforms (DNA origamis). As expected, constraining distances between DNA strands leads to faster reaction rates. However, it also induces side-effects that are not detectable in the solution-phase version of this circuitry. Appropriate design of the system, including protection and asymmetry between input and fuel strands, leads to a reproducible behaviour, at least one order of magnitude faster than the one observed under bulk conditions. Electronic supplementary information (ESI) available. See DOI: 10.1039/C5NR02434J

Fundamental Researches on the High-speed and High-efficiency Steelmaking Reaction

NASA Astrophysics Data System (ADS)

Kitamura, Shin-ya; Shibata, Hiroyuki; Maruoka, Nobuhiro

2012-06-01

Traditionally, steelmaking reactions have been analyzed by thermodynamics. Recently, software packages that can be used to calculate the equilibrium conditions have improved greatly. In some cases, information obtained in this software is useful for analyzing the steelmaking reaction. On the other hand, in industrial operation, steelmaking reactions, i.e., decarburization, dephosphorization, desulfurization or nitrogen removal, do not reach the equilibrium condition. Therefore, the kinetic model is very important for gaining a theoretical understanding of the steelmaking reaction. In this paper, the following recent research activities were shown; 1) mass transfer of impurities between solid oxide and liquid slag, 2) simulation model of hot metal dephosphorization by multiphase slag, 3) evaluation of reaction rate at bath surface in gas-liquid reaction system and 4) condition for forming of metal emulsion by bottom bubbling.

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.

Subsurface conditions in hydrothermal vents inferred from diffuse flow composition, and models of reaction and transport

NASA Astrophysics Data System (ADS)

Larson, B. I.; Houghton, J. L.; Lowell, R. P.; Farough, A.; Meile, C. D.

2015-08-01

Chemical gradients in the subsurface of mid-ocean ridge hydrothermal systems create an environment where minerals precipitate and dissolve and where chemosynthetic organisms thrive. However, owing to the lack of easy access to the subsurface, robust knowledge of the nature and extent of chemical transformations remains elusive. Here, we combine measurements of vent fluid chemistry with geochemical and transport modeling to give new insights into the under-sampled subsurface. Temperature-composition relationships from a geochemical mixing model are superimposed on the subsurface temperature distribution determined using a heat flow model to estimate the spatial distribution of fluid composition. We then estimate the distribution of Gibb's free energies of reaction beneath mid oceanic ridges and by combining flow simulations with speciation calculations estimate anhydrite deposition rates. Applied to vent endmembers observed at the fast spreading ridge at the East Pacific Rise, our results suggest that sealing times due to anhydrite formation are longer than the typical time between tectonic and magmatic events. The chemical composition of the neighboring low temperature flow indicates relatively uniform energetically favorable conditions for commonly inferred microbial processes such as methanogenesis, sulfate reduction and numerous oxidation reactions, suggesting that factors other than energy availability may control subsurface microbial biomass distribution. Thus, these model simulations complement fluid-sample datasets from surface venting and help infer the chemical distribution and transformations in subsurface flow.

Silica-promoted Diels-Alder reactions in carbon dioxide from gaseous to supercritical conditions

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

Weinstein, R.D.; Renslo, A.R.; Danheiser, R.L.

1999-04-15

Amorphous fumed silica (SiO{sub 2}) was shown to increase yields and selectivities of several Diels-Alder reactions in gaseous and supercritical CO{sub 2}. Pressure effects on the Diels-Alder reaction were explored using methyl vinyl ketone and penta-1,3-diene at 80 C. The selectivity of the reaction was not affected by pressure/density. As pressure was increased, the yield decreased. At the reaction temperature, adsorption isotherms at various pressures were obtained for the reactants and the Diels-Alder adduct. As expected when pressure is increased, the ratio of the amount of reactants adsorbed to the amount of reactants in the fluid phase decreases, thus causingmore » the yield to decrease. The Langmuir adsorption model fit the adsorption data. The Langmuir equilibrium partitioning constants all decreased with increasing pressure. The effect of temperature on adsorption was experimentally determined and traditional heats of adsorption were calculated. However, since supercritical CO{sub 2} is a highly compressible fluid, it is logical to examine the effect of temperature at constant density. In this case, entropies of adsorption were obtained. The thermodynamic properties that influence the real enthalpy and entropy of adsorption were derived. Methods of doping the silica and improving yields and selectivities were also explored.« less

Chemical Memory Reactions Induced Bursting Dynamics in Gene Expression

PubMed Central

Tian, Tianhai

2013-01-01

Memory is a ubiquitous phenomenon in biological systems in which the present system state is not entirely determined by the current conditions but also depends on the time evolutionary path of the system. Specifically, many memorial phenomena are characterized by chemical memory reactions that may fire under particular system conditions. These conditional chemical reactions contradict to the extant stochastic approaches for modeling chemical kinetics and have increasingly posed significant challenges to mathematical modeling and computer simulation. To tackle the challenge, I proposed a novel theory consisting of the memory chemical master equations and memory stochastic simulation algorithm. A stochastic model for single-gene expression was proposed to illustrate the key function of memory reactions in inducing bursting dynamics of gene expression that has been observed in experiments recently. The importance of memory reactions has been further validated by the stochastic model of the p53-MDM2 core module. Simulations showed that memory reactions is a major mechanism for realizing both sustained oscillations of p53 protein numbers in single cells and damped oscillations over a population of cells. These successful applications of the memory modeling framework suggested that this innovative theory is an effective and powerful tool to study memory process and conditional chemical reactions in a wide range of complex biological systems. PMID:23349679

Characterization of a Pressure-Fed LOX/LCH4 Reaction Control System Under Simulated Altitude and Thermal Vacuum Conditions

NASA Technical Reports Server (NTRS)

Atwell, Matthew J.; Melcher, John C.; Hurlbert, Eric A.; Morehead, Robert L.

2017-01-01

A liquid oxygen, liquid methane (LOX/LCH4) reaction control system (RCS) was tested at NASA Glenn Research Center's Plum Brook Station in the Spacecraft Propulsion Research Facility (B-2) under simulated altitude and thermal vacuum conditions. The RCS is a subsystem of the Integrated Cryogenic Propulsion Test Article (ICPTA) and was initially developed under Project Morpheus. Composed of two 28 lbf-thrust and two 7 lbf-thrust engines, the RCS is fed in parallel with the ICPTA main engine from four propellant tanks. 40 tests consisting of 1,010 individual thruster pulses were performed across 6 different test days. Major test objectives were focused on system dynamics, and included characterization of fluid transients, manifold priming, manifold thermal conditioning, thermodynamic vent system (TVS) performance, and main engine/RCS interaction. Peak surge pressures from valve opening and closing events were examined. It was determined that these events were impacted significantly by vapor cavity formation and collapse. In most cases the valve opening transient was more severe than the valve closing. Under thermal vacuum conditions it was shown that TVS operation is unnecessary to maintain liquid conditions at the thruster inlets. However, under higher heat leak environments the RCS can still be operated in a self-conditioning mode without overboard TVS venting, contingent upon the engines managing a range of potentially severe thermal transients. Lastly, during testing under cold thermal conditions the engines experienced significant ignition problems. Only after warming the thruster bodies with a gaseous nitrogen purge to an intermediate temperature was successful ignition demonstrated.

Kinetics and Mechanism of the Reaction of Hydoxyl Radicals with Acetonitrile under Atmospheric Conditions

NASA Technical Reports Server (NTRS)

Hynes, A. J.; Wine, P. H.

1997-01-01

The pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to determine absolute rate coefficients for the reaction OH + CH3CN (1) and its isotopic variants, OH + CD3CN (2), OD + CH3CN (3), and OD + CD3CN (4). Reactions 1 and 2 were studied as a function of pressure and temperature in N2, N2/O2, and He buffer gases. In the absence of O2 all four reactions displayed well-behaved kinetics with exponential OH decays and pseudo-first rate constants which were proportional to substrate concentration. Data obtained in N2 over the range 50-700 Torr at 298 K are consistent with k(sub 1), showing a small pressure dependence. The Arrhenius expression obtained by averaging data at all pressures in k(sub 1)(T) = (1.1(sup +0.5)/(sub -0.3)) x 10(exp -12) exp[(-1130 +/- 90)/T] cu cm /(molecule s). The kinetics of reaction 2 are found to be pressure dependent with k(sub 2) (298 K) increasing from (1.21 +/- 0.12) x 10(exp -14) to (2.16 +/- 0.11) x 10(exp -14) cm(exp 3)/ (molecule s) over the pressure range 50-700 Torr of N2 at 298 K. Data at pressures greater than 600 Torr give k(sub 2)(T) = (9.4((sup +13.4)(sub -5.0))) x 10(exp -13) exp[(-1180 +/- 250)/T] cu cm/(molecule s). The rates of reactions 3 and 4 are found to be independent of pressure over the range 50-700 Torr of N2 with 298 K rate coefficient given by k(sub 3) =(3.18 +/- 0.40) x 10(exp -14) cu cm/(molecule s) and k(sub 4) = (2.25 +/-0.28) x 10(exp -14) cu cm/(molecule s). In the presence of O2 each reaction shows complex (non-pseudo-first-order) kinetic behavior and/or an apparent decrease in the observed rate constant with increasing [O2], indicating the presence of significant OH or OD regeneration. Observation of regeneration of OH in (2) and OD in (3) is indicative of a reaction channel which proceeds via addition followed by reaction of the adduct, or one of its decomposition products, with O2. The observed OH and OD decay profiles have been modeled by using a simple mechanistic

Catalytic Conia-ene and related reactions.

PubMed

Hack, Daniel; Blümel, Marcus; Chauhan, Pankaj; Philipps, Arne R; Enders, Dieter

2015-10-07

Since its initial inception, the Conia-ene reaction, known as the intramolecular addition of enols to alkynes or alkenes, has experienced a tremendous development and appealing catalytic protocols have emerged. This review fathoms the underlying mechanistic principles rationalizing how substrate design, substrate activation, and the nature of the catalyst work hand in hand for the efficient synthesis of carbocycles and heterocycles at mild reaction conditions. Nowadays, Conia-ene reactions can be found as part of tandem reactions, and the road for asymmetric versions has already been paved. Based on their broad applicability, Conia-ene reactions have turned into a highly appreciated synthetic tool with impressive examples in natural product synthesis reported in recent years.

Investigation of influence of hypomagnetic conditions closely similar to interplanetary magnetic filed on behavioral and vegetative reactions of higher mammals

NASA Astrophysics Data System (ADS)

Krivova, Natalie; Trukhanov, Kiril; Zamotshina, Tatyana; Zaeva, Olga; Khodanovich, Marina; Misina, Tatyana; Tukhvatulin, Ravil; Suhko, Valery

To study the influence of long being under reduced magnetic field on behavioral and vegetative reactions of higher mammals the white rat males were put into the 700-1000 times reduced geomagnetic field (50-70 nT) for 25 days. Such field was obtained by using automatic compensation of the horizontal and vertical components of the GMF at a frequencies up to 10 Hz by means of solenoids of the experimental magnetic system. Control animals were located in the same room under usual laboratory GMF conditions (52 uT). Two days before the experiment the behavioral reactions were studied in the "open field" by means of a set of tests, characterizing the level of emotionality, moving and orientational-investigative activities of the animals under conditions of unimpeded behavior. 60 white underbred rat males with the initial body mass of 200 g were divided into three clusters. Animals with average indices were selected for the experiment. We have judged behavioral reaction disturbances of the rats under hypomagnetic conditions using videotape recordings carried out in the entire course of the chronic experiment. According to the obtained results during the period of maximum activity (from 230 to 330 a.m.) the number of interrelations between the individuals increased appreciably for experimental rats including interrelations with aggressive character. This was real during all 25 days of observation. We observed a certain dynamics of this index differed from that of the control group. We have also analyzed the final period of observation from the 21th to the 25th days. In this period we studied the 24 hours' dynamics of interrelations which were noted during 5 minutes in every hour around the clock. In the control group the number of interrelation was at a constantly low level. For experimental animals the number of interrelations was higher in the night hours than in the day ones. Moreover it exceeded the similar indexes observed from the 1st to the 20th day. For example from

Lithium cell reactions

NASA Astrophysics Data System (ADS)

Clark, W.; Dampier, F.; McDonald, R.; Lombardi, A.; Batson, D.

1985-02-01

The objectives of Part 1 of this program were to: (1) investigate reactions occurring in the Li/SOCl2 cell for a range of specified test conditions, and (2) to perform analyses to identify reactants, intermediates and products generated by the chemical and electrochemical reactions occuring in the cell and to assess their impact upon safety and performance. The stoichiometry of the SOCl2 reduction reaction was investigated in 0.6 Ahr prototype cells by extracting the cells five times with pure SOCl2, after discharge then analyzing the combined extracts for SO2 by quantitative IR spectroscopy. The cells had high electrolyte-to-carbon mass ratios comparable to those in commercial cells. The multiple SOCl2 extraction procedure was developed to recover the SO2 discharge product adsorbed on the high surface area carbon electrode.

Microwave-Assisted Condensation Reactions of Acetophenone Derivatives and Activated Methylene Compounds with Aldehydes Catalyzed by Boric Acid under Solvent-Free Conditions.

PubMed

Brun, Elodie; Safer, Abdelmounaim; Carreaux, François; Bourahla, Khadidja; L'helgoua'ch, Jean-Martial; Bazureau, Jean-Pierre; Villalgordo, Jose Manuel

2015-06-23

We here disclosed a new protocol for the condensation of acetophenone derivatives and active methylene compounds with aldehydes in the presence of boric acid under microwave conditions. Implementation of the reaction is simple, healthy and environmentally friendly owing to the use of a non-toxic catalyst coupled to a solvent-free procedure. A large variety of known or novel compounds have thus been prepared, including with substrates bearing acid or base-sensitive functional groups.

Effects of modified short-leg walkers on ground reaction force characteristics.

PubMed

Keefer, Maria; King, Jon; Powell, Douglas; Krusenklaus, John H; Zhang, Songning

2008-11-01

Although short-leg walkers are often used in the treatment of lower extremity injuries (ankle and foot fractures and severe ankle sprains), little is known about the effect the short-leg walker on gait characteristics. The purpose was to examine how heel height modifications in different short-leg walkers and shoe side may affect ground reaction forces in walking. Force platforms were used to collect ground reaction force data on 10 healthy participants. Five trials were performed in each of six conditions: lab shoes, gait walker, gait walker with heel insert on shoe side, gait walker modified with insert on walker side, equalizer walker, and equalizer walker with heel insert on shoe side. Conditions were randomized and walking speed was standardized between conditions. A 2x6 (sidexcondition) repeated analysis of variance was used on selected ground reaction force variables (P<0.05). The application of a walker created peak vertical and anteroposterior ground reaction forces prior to the normal peaks associated with the loading response. Wearing a walker introduced an elevated minimum vertical ground reaction force in all conditions except the equalizer walker when compared to shoe on the shoe side. Peak propulsive anteroposterior ground reaction forces were smaller in all walker conditions compared to shoe on walker side. The application of heel insert in gait walker with heel insert (on shoe side) and gait walker modified (on walker side) does not diminish the minimum vertical ground reaction force as hypothesized. Wearing a walker decreases the peak propulsive anteroposterior ground reaction force on the walker side and induces asymmetrical loading.

Microfluidic study of fast gas-liquid reactions.

PubMed

Li, Wei; Liu, Kun; Simms, Ryan; Greener, Jesse; Jagadeesan, Dinesh; Pinto, Sascha; Günther, Axel; Kumacheva, Eugenia

2012-02-15

We present a new concept for studies of the kinetics of fast gas-liquid reactions. The strategy relies on the microfluidic generation of highly monodisperse gas bubbles in the liquid reaction medium and subsequent analysis of time-dependent changes in bubble dimensions. Using reactions of CO(2) with secondary amines as an exemplary system, we demonstrate that the method enables rapid determination of reaction rate constant and conversion, and comparison of various binding agents. The proposed approach addresses two challenges in studies of gas-liquid reactions: a mass-transfer limitation and a poorly defined gas-liquid interface. The proposed strategy offers new possibilities in studies of the fundamental aspects of rapid multiphase reactions, and can be combined with throughput optimization of reaction conditions.

Cardiovascular and cortisol reactions to acute psychological stress under conditions of high versus low social evaluative threat: associations with the type D personality construct.

PubMed

Bibbey, Adam; Carroll, Douglas; Ginty, Annie T; Phillips, Anna C

2015-06-01

Social evaluative threat is an important factor in the cardiovascular response to mental stress. This study examined whether Type D personality, characterized by social inhibition and negative affectivity, is associated with an adverse cardiovascular response to a non-social and social evaluative threat. A total of 2300 students were screened for Type D personality, and 130 were selected for a nonsocial stress exposure condition (31 Type D, 30 non-Type D: 52% female) or a condition high in social evaluative threat (35 Type D, 34 non-Type D: 55% female). Systolic (SBP) and diastolic blood pressure (DBP), heart rate (HR), and salivary cortisol were measured. Social evaluative threat resulted in higher cardiovascular responses than the nonsocial challenge (SBP, p = .001, η = 0.092;DBP, p = .006, η = 0.058;HR, p = .006, η = 0.059). The greatest cardiovascular stress reactions were exhibited by Type D participants in the high social evaluation condition; reflected in significant group by condition interactions for SBP (F(1,126) = 7.29, p = .008, η = 0.055), DBP (F(1,126) = 5.23, p = .024, η = 0.040), and HR (F(1,126) = 5.04, p = .027, η = 0.038) reactivity. Only Type Ds in the social condition mounted a positive cortisol response (F(1,33) = 5.07, p = .031, η = 0.133). Type D individuals show different stress reactions depending on the social evaluative nature of the stress exposure. These findings suggest that dysregulation of the stress response in social situations potentially increases cardiovascular disease risk.

Severe Cutaneous Drug Reactions: Do Overlapping Forms Exist?

PubMed

Horcajada-Reales, C; Pulido-Pérez, A; Suárez-Fernández, R

2016-01-01

Acute generalized exanthematous pustulosis, Stevens-Johnson syndrome, toxic epidermal necrolysis, and drug reaction with eosinophilia and systemic symptoms are all severe hypersensitivity reactions to medications. While each of these reactions is a well-established entity with specific diagnostic criteria, clinicians see cases that fulfill criteria for more than one form, prompting discussion on the possibility of combined forms. Such overlapping clinical pictures meeting the criteria for 2 conditions have thus become a topic of debate in dermatology in recent years. We describe 2 patients with cutaneous drug reactions having the characteristics of both acute generalized exanthematous pustulosis and Stevens-Johnson syndrome -toxic epidermal necrolysis. We also review previously published cases and current thinking on such overlapping conditions. Copyright © 2015 Elsevier España, S.L.U. and AEDV. All rights reserved.

Automatized Assessment of Protective Group Reactivity: A Step Toward Big Reaction Data Analysis.

PubMed

Lin, Arkadii I; Madzhidov, Timur I; Klimchuk, Olga; Nugmanov, Ramil I; Antipin, Igor S; Varnek, Alexandre

2016-11-28

We report a new method to assess protective groups (PGs) reactivity as a function of reaction conditions (catalyst, solvent) using raw reaction data. It is based on an intuitive similarity principle for chemical reactions: similar reactions proceed under similar conditions. Technically, reaction similarity can be assessed using the Condensed Graph of Reaction (CGR) approach representing an ensemble of reactants and products as a single molecular graph, i.e., as a pseudomolecule for which molecular descriptors or fingerprints can be calculated. CGR-based in-house tools were used to process data for 142,111 catalytic hydrogenation reactions extracted from the Reaxys database. Our results reveal some contradictions with famous Greene's Reactivity Charts based on manual expert analysis. Models developed in this study show high accuracy (ca. 90%) for predicting optimal experimental conditions of protective group deprotection.

Do Geriatric Conditions Increase Risk of Adverse Drug Reactions in Ambulatory Elders? Results From the VA GEM Drug Study

PubMed Central

Hanlon, Joseph T.; Sloane, Richard J.; Boscardin, W. John; Schmader, Kenneth E.

2011-01-01

Background. Many clinicians prescribe cautiously to older adults with common geriatric conditions for fear of causing adverse drug reactions (ADRs). However, little is known about the association between these conditions and risk of ADRs. Methods. Using data from the VA Geriatric Evaluation and Management Drug Study, we determined any, preventable, and serious ADRs in 808 elders for 12 months after hospital discharge using a validated process involving patient self-report and chart review adjudicated by two health care professionals. Eight common geriatric conditions (activities of daily living, dementia, incontinence, falls, difficulty ambulating, malnourishment, depression, and prolonged bed rest) were evaluated at study baseline through self-report and structured assessments. We used Poisson regression to model the relationship between these geriatric conditions and ADRs. Results. Participants had a mean of 2.9 ± 1.2 geriatric conditions. Over the 12-month follow-up period, 497 ADRs occurred in 269 participants, including 187 ADRs considered preventable and 127 considered severe. On multivariable analyses, participants with dependency in one or more activities of daily living were less likely to suffer ADRs than those who were fully independent (incidence rate ratio: 0.78, 95% confidence interval = 0.62–1.00). None of the other seven geriatric conditions assessed were associated with ADR risk. Results were similar for preventable and serious ADRs, although participants with a history of falls were more likely to develop serious ADRs (incidence rate ratio: 1.49, 95% confidence interval = 1.00–2.21). Conclusions. Many geriatric conditions were not associated with risk of ADRs. Although it is prudent to prescribe judiciously in patients with these conditions, excessive caution may not be warranted. PMID:21321003

Iminium and enamine catalysis in enantioselective photochemical reactions.

PubMed

Zou, You-Quan; Hörmann, Fabian M; Bach, Thorsten

2018-01-22

Although enantioselective catalysis under thermal conditions has been well established over the last few decades, the enantioselective catalysis of photochemical reactions is still a challenging task resulting from the complex enantiotopic face differentiation in the photoexcited state. Recently, remarkable achievements have been reported by a synergistic combination of organocatalysis and photocatalysis, which have led to the expedient construction of a diverse range of enantioenriched molecules which are generally not easily accessible under thermal conditions. In this tutorial review, we summarize and highlight the most significant advances in iminium and enamine catalysis of enantioselective photochemical reactions, with an emphasis on catalytic modes and reaction types.

Iminium and enamine catalysis in enantioselective photochemical reactions

PubMed Central

Hörmann, Fabian M.

2018-01-01

Although enantioselective catalysis under thermal conditions has been well established over the last few decades, the enantioselective catalysis of photochemical reactions is still a challenging task resulting from the complex enantiotopic face differentiation in the photoexcited state. Recently, remarkable achievements have been reported by a synergistic combination of organocatalysis and photocatalysis, which have led to the expedient construction of a diverse range of enantioenriched molecules which are generally not easily accessible under thermal conditions. In this tutorial review, we summarize and highlight the most significant advances in iminium and enamine catalysis of enantioselective photochemical reactions, with an emphasis on catalytic modes and reaction types. PMID:29155908

Possibility of the Nonenzymatic Browning (Maillard) Reaction in the ISM

NASA Astrophysics Data System (ADS)

Jalbout, Abraham F.; Shipar, M. Abul Haider

2008-04-01

The possibility of the occurrence of the nonenzymatic browning reaction in the gaseous phase in the interstellar medium has been investigated by using Density Functional Theory computations. Mechanisms for the reactions between formaldehyde ( Fald) + glycine ( Gly), Fald + NH 3 and Fald + methylamine ( MeAm) have been proposed, and the possibility of the formation of different compounds in the proposed mechanisms has been evaluated through calculating the Gibb's free energy changes for different steps of the reaction, by following the total mass balance. The Fald + Gly reaction under basic conditions is found as the most favorable for producing 1-methyl-amino methene or 1-methyl-amino methelene ( MAM). The reaction under acidic conditions is found to be the least favorable for producing MAM. The Fald + NH 3 reaction is found to be plausible for the production of MeAm, which can participate by reaction with Fald, resulting in the formation of MAM.

Encouraging Conceptual Change: The Use of Bridging Analogies in the Teaching of Action-Reaction Forces and the "At Rest" Condition in Physics. Research Report

ERIC Educational Resources Information Center

Bryce, Tom; MacMillan, Kenneth

2005-01-01

The qualitative study described in this paper examined the effectiveness of bridging analogies intended to bring about conceptual change as part of a constructivist approach to teaching about action-reaction forces in the 'at rest' condition in physics. Twenty-one 15-year-old students were involved in the investigation with subgroups previously…

Resonances in the cumulative reaction probability for a model electronically nonadiabatic reaction

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

Qi, J.; Bowman, J.M.

1996-05-01

The cumulative reaction probability, flux{endash}flux correlation function, and rate constant are calculated for a model, two-state, electronically nonadiabatic reaction, given by Shin and Light [S. Shin and J. C. Light, J. Chem. Phys. {bold 101}, 2836 (1994)]. We apply straightforward generalizations of the flux matrix/absorbing boundary condition approach of Miller and co-workers to obtain these quantities. The upper adiabatic electronic potential supports bound states, and these manifest themselves as {open_quote}{open_quote}recrossing{close_quote}{close_quote} resonances in the cumulative reaction probability, at total energies above the barrier to reaction on the lower adiabatic potential. At energies below the barrier, the cumulative reaction probability for themore » coupled system is shifted to higher energies relative to the one obtained for the ground state potential. This is due to the effect of an additional effective barrier caused by the nuclear kinetic operator acting on the ground state, adiabatic electronic wave function, as discussed earlier by Shin and Light. Calculations are reported for five sets of electronically nonadiabatic coupling parameters. {copyright} {ital 1996 American Institute of Physics.}« less

A rapid, automated approach to optimisation of multiple reaction monitoring conditions for quantitative bioanalytical mass spectrometry.

PubMed

Higton, D M

2001-01-01

An improvement to the procedure for the rapid optimisation of mass spectrometry (PROMS), for the development of multiple reaction methods (MRM) for quantitative bioanalytical liquid chromatography/tandem mass spectrometry (LC/MS/MS), is presented. PROMS is an automated protocol that uses flow-injection analysis (FIA) and AppleScripts to create methods and acquire the data for optimisation. The protocol determines the optimum orifice potential, the MRM conditions for each compound, and finally creates the MRM methods needed for sample analysis. The sensitivities of the MRM methods created by PROMS approach those created manually. MRM method development using PROMS currently takes less than three minutes per compound compared to at least fifteen minutes manually. To further enhance throughput, approaches to MRM optimisation using one injection per compound, two injections per pool of five compounds and one injection per pool of five compounds have been investigated. No significant difference in the optimised instrumental parameters for MRM methods were found between the original PROMS approach and these new methods, which are up to ten times faster. The time taken for an AppleScript to determine the optimum conditions and build the MRM methods is the same with all approaches. Copyright 2001 John Wiley & Sons, Ltd.

Uranium plasma emission at gas-core reaction conditions

NASA Technical Reports Server (NTRS)

Williams, M. D.; Jalufka, N. W.; Hohl, F.; Lee, J. H.

1976-01-01

The results of uranium plasma emission produced by two methods are reported. For the first method a ruby laser was focused on the surface of a pure U-238 sample to create a plasma plume with a peak plasma density of about 10 to the 20th power/cu cm and a temperature of about 38,600 K. The absolute intensity of the emitted radiation, covering the range from 300 to 7000 A was measured. For the second method, the uranium plasma was produced in a 20 kilovolt, 25 kilojoule plasma-focus device. The 2.5 MeV neutrons from the D-D reaction in the plasma focus are moderated by polyethylene and induce fissions in the U-235. Spectra of both uranium plasmas were obtained over the range from 30 to 9000 A. Because of the low fission yield the energy input due to fissions is very small compared to the total energy in the plasma.

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

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

Boron Heterocycle High-Fidelity Estrogen Mimics as Novel Antiestrogens for the Treatment of Breast Cancer

DTIC Science & Technology

2001-10-01

fungi, viruses) bacteriostat- ic germicide triclosan 98--1 0 and even, oddly enough, the well-known antituberculosis drug isoniazid. INS(1,4,5)P3 RECEPTOR...and its Compounds. Irvine, California. September ticular reference to athletes. Nutr Health 1999;13:31-37. 16-17, 1992 (proceedings.). Environ Health...derivatives and analogues. J Med Chem 98. McMurry LM, Oethinger M, Levy SB: Triclosan targets 1984;27:947-953. lipid synthesis. Nature 1998;394:531-532. 84

Experimental Study of Serpentinization Reactions

NASA Technical Reports Server (NTRS)

Cohen, B. A.; Brearley, A. J.; Ganguly, J.; Liermann, H.-P.; Keil, K.

2004-01-01

Current carbonaceous chondrite parent-body thermal models [1-3] produce scenarios that are inconsistent with constraints on aqueous alteration conditions based on meteorite mineralogical evidence, such as phase stability relationships within the meteorite matrix minerals [4] and isotope equilibration arguments [5, 6]. This discrepancy arises principally because of the thermal runaway effect produced by silicate hydration reactions (here loosely called serpentinization, as the principal products are serpentine minerals), which are so exothermic as to produce more than enough heat to melt more ice and provide a self-sustaining chain reaction. One possible way to dissipate the heat of reaction is to use a very small parent body [e.g., 2] or possibly a rubble pile model. Another possibility is to release this heat more slowly, which depends on the alteration reaction path and kinetics.

Reactions of C1 Building Blocks

NASA Astrophysics Data System (ADS)

Stöcker, Michael

The chapter “Reactions of C1 Building Blocks” covers the direct conversion of methane to aromatics, the methanol-to-hydrocarbons (MTHC) conversion with respect to gasoline (methanol to gasoline) and olefins (methanol to olefins, methanol-to-propene) as well as some combinations like the TIGAS and Mobil's olefin-to-gasoline and distillate processes. The main focus within this chapter will be on the industrial processes, especially concerning the MTHC reactions - including catalytic systems, reaction conditions, process - and to a minor extent related to the mechanistic aspects and kinetic considerations.

Nonequilibrium thermodynamics and boundary conditions for reaction and transport in heterogeneous media

NASA Astrophysics Data System (ADS)

Gaspard, Pierre; Kapral, Raymond

2018-05-01

Nonequilibrium interfacial thermodynamics is formulated in the presence of surface reactions for the study of diffusiophoresis in isothermal systems. As a consequence of microreversibility and Onsager-Casimir reciprocal relations, diffusiophoresis, i.e., the coupling of the tangential components of the pressure tensor to the concentration gradients of solute species, has a reciprocal effect where the interfacial currents of solutes are coupled to the slip velocity. The presence of surface reactions is shown to modify the diffusiophoretic and reciprocal effects at the fluid-solid interface. The thin-layer approximation is used to describe the solution flowing near a reactive solid interface. Analytic formulas describing the diffusiophoretic and reciprocal effects are deduced in the thin-layer approximation and tested numerically for the Poiseuille flow of a solution between catalytic planar surfaces.

Atherton–Todd reaction: mechanism, scope and applications

PubMed Central

Le Corre, Stéphanie S; Berchel, Mathieu; Couthon-Gourvès, Hélène; Haelters, Jean-Pierre

2014-01-01

Summary Initially, the Atherton–Todd (AT) reaction was applied for the synthesis of phosphoramidates by reacting dialkyl phosphite with a primary amine in the presence of carbon tetrachloride. These reaction conditions were subsequently modified with the aim to optimize them and the reaction was extended to different nucleophiles. The mechanism of this reaction led to controversial reports over the past years and is adequately discussed. We also present the scope of the AT reaction. Finally, we investigate the AT reaction by means of exemplary applications, which mainly concern three topics. First, we discuss the activation of a phenol group as a phosphate which allows for subsequent transformations such as cross coupling and reduction. Next, we examine the AT reaction applied to produce fire retardant compounds. In the last section, we investigate the use of the AT reaction for the production of compounds employed for biological applications. The selected examples to illustrate the applications of the Atherton–Todd reaction mainly cover the past 15 years. PMID:24991268

Chemical Reactions of Portland Cement with Aqueous CO2 and Their Impacts on Cement's Mechanical Properties under Geologic CO2 Sequestration Conditions.

PubMed

Li, Qingyun; Lim, Yun Mook; Flores, Katharine M; Kranjc, Kelly; Jun, Young-Shin

2015-05-19

To provide information on wellbore cement integrity in the application of geologic CO2 sequestration (GCS), chemical and mechanical alterations were analyzed for cement paste samples reacted for 10 days under GCS conditions. The reactions were at 95 °C and had 100 bar of either N2 (control condition) or CO2 contacting the reaction brine solution with an ionic strength of 0.5 M adjusted by NaCl. Chemical analyses showed that the 3.0 cm × 1.1 cm × 0.3 cm samples were significantly attacked by aqueous CO2 and developed layer structures with a total attacked depth of 1220 μm. Microscale mechanical property analyses showed that the hardness and indentation modulus of the carbonated layer were 2-3 times greater than for the intact cement, but those in the portlandite-dissolved region decreased by ∼50%. The strength and elastic modulus of the bulk cement samples were reduced by 93% and 84%, respectively. The properties of the microscale regions, layer structure, microcracks, and swelling of the outer layers combined to affect the overall mechanical properties. These findings improve understanding of wellbore integrity from both chemical and mechanical viewpoints and can be utilized to improve the safety and efficiency of CO2 storage.

Reaction of Basaltic Materials under High-Fidelity Venus Surface Conditions using the Glenn Extreme Environment Rig: First Results

NASA Technical Reports Server (NTRS)

Radoman-Shaw, Brandon; Harvey, Ralph; Costa, Gustavo; Nakley, Leah Michelle; Jacobson, Nathan S.

2016-01-01

Both historical and current investigations of Venus suggest that atmosphererock interactions play a critical role in the evolution of its atmosphere and crust. We have begun a series of systematic experiments designed to further our understanding of atmosphere-driven weathering and secondary mineralization of basaltic materials that may be occurring on Venus today. Our experiments expose representative igneous phases (mineral, glasses and rocks) to a high-fidelity simulation of Venus surface conditions using the NASA Glenn Extreme Environment Rig (GEER) located at the NASA Glenn Research Center in Cleveland, Ohio. GEER is a very large (800L) vessel capable of producing a long-term, high fidelity simulation of both the physical conditions (750 K and 92 bar) and atmospheric chemistry (down to the ppb-level) asso-ciated with the Venusian surface. As of this writing we have just finished the first of several planned experiments: a 42-day exposure of selected mineral, rocks and volcanic glasses. Our goal is to identify and prioritize the reactions taking place and better our understanding of their importance in Venus' climate history.

Diastereoselective intermolecular Pauson-Khand reactions of chiral cyclopropenes.

PubMed

Pallerla, Mahesh K; Fox, Joseph M

2005-08-04

In this Letter, it is demonstrated that the unusual reactivity of cyclopropenes can increase the scope and utility of intermolecular Pauson-Khand reactions. The well-defined chiral environment of cyclopropenes has a powerful influence on the diastereoselectivity of the reactions and leads to the production of a single cyclopentenone in each of the described cases. The cyclopropane ring strongly influences the stereochemistry of reactions at the enone, and the three-membered ring can subsequently be cleaved under mild conditions. [reaction: see text

Dynamic three-dimensional pore-scale imaging of reaction in a carbonate at reservoir conditions.

PubMed

Menke, Hannah P; Bijeljic, Branko; Andrew, Matthew G; Blunt, Martin J

2015-04-07

Quantifying CO2 transport and average effective reaction rates in the subsurface is essential to assess the risks associated with underground carbon capture and storage. We use X-ray microtomography to investigate dynamic pore structure evolution in situ at temperatures and pressures representative of underground reservoirs and aquifers. A 4 mm diameter Ketton carbonate core is injected with CO2-saturated brine at 50 °C and 10 MPa while tomographic images are taken at 15 min intervals with a 3.8 μm spatial resolution over a period of 2(1/2) h. An approximate doubling of porosity with only a 3.6% increase in surface area to volume ratio is measured from the images. Pore-scale direct simulation and network modeling on the images quantify an order of magnitude increase in permeability and an appreciable alteration of the velocity field. We study the uniform reaction regime, with dissolution throughout the core. However, at the pore scale, we see variations in the degree of dissolution with an overall reaction rate which is approximately 14 times lower than estimated from batch measurements. This work implies that in heterogeneous rocks, pore-scale transport of reactants limits dissolution and can reduce the average effective reaction rate by an order of magnitude.

First High Resolution IR Spectra of 2,2-D_{2}-PROPANE. the νb{15} (B_{1}) A-Type Band Near 954.709 \\wn. Determination of Ground and Upper State Constants.

NASA Astrophysics Data System (ADS)

Gjuraj, Daniel; Daunt, S. J.; Grzywacz, Robert; Lafferty, Walter; Flaud, Jean-Marie; Billinghurst, Brant E.

2017-06-01

As part of our project on the study of isotopologues of propane we have taken the spectra of the 2-D and 2,2-D_2 substituted species. There have been no studies of these species since the early IR studies. We recorded high resolution (Δν = 0.0009 \\wn) FTS data on the Canadian Light Source Far-IR beamline. The spectra of all bands of both species in the region examined (500 - 1250 \\wn) show torsionally perturbed lines, all but one band appearing globally perturbed. Virtually all bands were not amenable to analysis at present except for the νb{15} (B_{1}) A-type band centered at 954.709 \\wn. One can still see a few perturbed lines with torsional components but overall most lines were single and could be readily assigned using traditional methods. The spectrum is modelled well using PGOPHER. No MW determined GS constants were available so we have analyzed about 3500 levels to determine both ground state and upper state rotational constants. Friedman & Turkevich, J. Chem. Phys. 17, 1012 ff. (1949) McMurry, Thornton & Condon, J. Chem. Phys. 17, 918 ff. (1949) McMurry & Thornton, J. Chem. Phys. 19, 1014 ff.(1951) Gayles & King, Spectrochim. Acta 21, 543 ff.(1965) Kondo & Saeki, Spectrochim. Acta 29A, 735 ff. (1973) Western, J. Quant. Spectrosc. Rad. Transf. 186, 221 ff. (2017).

Incorporating reaction-rate dependence in reaction-front models of wellbore-cement/carbonated-brine systems

DOE PAGES

Iyer, Jaisree; Walsh, Stuart D. C.; Hao, Yue; ...

2017-03-08

Contact between wellbore cement and carbonated brine produces reaction zones that alter the cement's chemical composition and its mechanical properties. The reaction zones have profound implications on the ability of wellbore cement to serve as a seal to prevent the flow of carbonated brine. Under certain circumstances, the reactions may cause resealing of leakage pathways within the cement or at cement-interfaces; either due to fracture closure in response to mechanical weakening or due to the precipitation of calcium carbonate within the fracture. In prior work, we showed how mechanical sealing can be simulated using a diffusion-controlled reaction-front model that linksmore » the growth of the cement reaction zones to the mechanical response of the fracture. Here, we describe how such models may be extended to account for the effects of the calcite reaction-rate. We discuss how the relative rates of reaction and diffusion within the cement affect the precipitation of calcium carbonate within narrow leakage pathways, and how such behavior relates to the formation of characteristic reaction modes in the direction of flow. In addition, we compare the relative impact of precipitation and mechanical deformation on fracture sealing for a range of flow conditions and fracture apertures. Here, we conclude by considering how the prior leaching of calcium from cement may influence the sealing behavior of fractures, and the implication of prior leaching on the ability of laboratory tests to predict long-term sealing.« less

Incorporating reaction-rate dependence in reaction-front models of wellbore-cement/carbonated-brine systems

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

Iyer, Jaisree; Walsh, Stuart D. C.; Hao, Yue

Contact between wellbore cement and carbonated brine produces reaction zones that alter the cement's chemical composition and its mechanical properties. The reaction zones have profound implications on the ability of wellbore cement to serve as a seal to prevent the flow of carbonated brine. Under certain circumstances, the reactions may cause resealing of leakage pathways within the cement or at cement-interfaces; either due to fracture closure in response to mechanical weakening or due to the precipitation of calcium carbonate within the fracture. In prior work, we showed how mechanical sealing can be simulated using a diffusion-controlled reaction-front model that linksmore » the growth of the cement reaction zones to the mechanical response of the fracture. Here, we describe how such models may be extended to account for the effects of the calcite reaction-rate. We discuss how the relative rates of reaction and diffusion within the cement affect the precipitation of calcium carbonate within narrow leakage pathways, and how such behavior relates to the formation of characteristic reaction modes in the direction of flow. In addition, we compare the relative impact of precipitation and mechanical deformation on fracture sealing for a range of flow conditions and fracture apertures. Here, we conclude by considering how the prior leaching of calcium from cement may influence the sealing behavior of fractures, and the implication of prior leaching on the ability of laboratory tests to predict long-term sealing.« less

The Reaction and Regeneration of Cementum in Various Pathological Conditions : (Section of Odontology).

PubMed

Stones, H H

1934-04-01

(1) The reaction of cementum and its adjoining tissues to induced pathological conditions associated with the gingival sulcus is described.(2) After subjecting the sulcus to interference, its histological appearance is compared with that of definite parodontal disease.(3) Various methods were adopted for these experiments, which were performed on monkeys.(4) Artificial pockets were produced by detaching the subgingival epithelium and underlying connective tissue from the cementum. (a) Cementum is easily removed accidentally, when scraping monkeys' teeth. (b) Reattachment of connective tissues to cementum is effected, but is usually incomplete. (c) Epithelium always firmly reunites with cementum. (d) The artificial sulcus which is usually deeper than normal does not show, microscopically, the same pathological changes as in parodontal disease.(5) In other experiments, in addition to deepening the sulcus, the cementum lining the pockets was also removed, leaving denuded dentine in contact with the connective tissue. A similar condition was achieved by another method in which a dental bur was inserted between two teeth below the gum margin. (a) The gingival epithelium is capable of forming a weak attachment to the dentine, though this does not usually occur. It always proliferates down and unites with the nearest layer of cementum. It seems to have a peculiar affinity for this tissue. (b) Underlying connective tissue does not usually unite with the dentine. When this happens it is effected by the regeneration of cementum, this new tissue being lined by new cementoblasts. (c) The width of the periodontal membrane, which was increased by the experiment, is reduced to a more normal level by deposition of new alveolar bone, and to a lesser extent by regeneration of cementum. (d) In this series of experiments the artificial pocket is permanent and somewhat resembles that of parodontal disease. This is probably due, not so much to the injury, but to its effects creating a

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.

The hexadehydro-Diels-Alder reaction.

PubMed

Hoye, Thomas R; Baire, Beeraiah; Niu, Dawen; Willoughby, Patrick H; Woods, Brian P

2012-10-11

Arynes (aromatic systems containing, formally, a carbon-carbon triple bond) are among the most versatile of all reactive intermediates in organic chemistry. They can be 'trapped' to give products that are used as pharmaceuticals, agrochemicals, dyes, polymers and other fine chemicals. Here we explore a strategy that unites the de novo generation of benzynes-through a hexadehydro-Diels-Alder reaction-with their in situ elaboration into structurally complex benzenoid products. In the hexadehydro-Diels-Alder reaction, a 1,3-diyne is engaged in a [4+2] cycloisomerization with a 'diynophile' to produce the highly reactive benzyne intermediate. The reaction conditions for this simple, thermal transformation are notable for being free of metals and reagents. The subsequent and highly efficient trapping reactions increase the power of the overall process. Finally, we provide examples of how this de novo benzyne generation approach allows new modes of intrinsic reactivity to be revealed.

Food Protein-polysaccharide Conjugates Obtained via the Maillard Reaction: A Review.

PubMed

de Oliveira, Fabíola Cristina; Coimbra, Jane Sélia Dos Reis; de Oliveira, Eduardo Basílio; Zuñiga, Abraham Damian Giraldo; Rojas, Edwin E Garcia

2016-05-18

The products formed by glycosylation of food proteins with carbohydrates via the Maillard reaction, also known as conjugates, are agents capable of changing and improving techno-functional characteristics of proteins. The Maillard reaction uses the covalent bond between a group of a reducing carbohydrates and an amino group of a protein. This reaction does not require additional chemicals as it occurs naturally under controlled conditions of temperature, time, pH, and moisture. Moreover, there is growing interest in modifying proteins for industrial food applications. This review analyses the current state of art of the Maillard reaction on food protein functionalities. It also discusses the influence of the Maillard reaction on the conditions and formulation of reagents that improve desirable techno-functional characteristics of food protein.

Activity of Co-N multi walled carbon nanotubes electrocatalysts for oxygen reduction reaction in acid conditions

NASA Astrophysics Data System (ADS)

Osmieri, Luigi; Monteverde Videla, Alessandro H. A.; Specchia, Stefania

2015-03-01

Two catalysts are synthesized by wet impregnation of multi walled carbon nanotubes (MWCNT) with a complex formed between Co(II) ions and the nitrogen-containing molecule 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPTZ), followed by one or two identical heat treatments in N2 atmosphere at 800 °C for 3 h. Catalysts are fully characterized by FESEM, EDX, BET, XRD, FTIR, TGA, XPS analyses, and electrochemical techniques. The electrocatalytic activity towards oxygen reduction reaction (ORR) of the catalysts in acid conditions is assessed by means of a rotating disk electrode (RDE) apparatus and a specific type of cell equipped with a gas diffusion working electrode (GDE). In both testing approaches, the catalyst heat-treated twice (Co-N/MWCNT-2) exhibits higher electroactivity than the catalyst heat-treated once (Co-N/MWCNT-1). Chronoamperometries both in RDE and GDE cell are also performed, showing less electroactivity decay and better current performance for the catalyst heat-treated twice.

Role of Microbes in the Smectite-to-Illite Reaction

USGS Publications Warehouse

Kim, J.; Dong, H.; Seabaugh, J.; Newell, Steven W.; Eberl, D.D.

2004-01-01

Temperature, pressure, and time have been thought to control the smectiteto-illite (S-I) reaction, an important diagenetic process used for petroleum exploration. We demonstrated that microorganisms can promote the S-I reaction by dissolving smectite through reduction of structural FE(III) at room temperature and 1 atmosphere within 14 days. This reaction typically requires conditions of 300?? to 350??C, 100 megapascals, and 4 to 5 months in the absence of microbial activity. These results challenge the conventional concept of the S-I reaction and of reaction kinetic models.

Role of microbes in the smectite-to-illite reaction

NASA Technical Reports Server (NTRS)

Kim, Jinwook; Dong, Hailiang; Seabaugh, Jennifer; Newell, Steven W.; Eberl, Dennis D.

2004-01-01

Temperature, pressure, and time have been thought to control the smectite-to-illite (S-I) reaction, an important diagenetic process used for petroleum exploration. We demonstrated that microorganisms can promote the S-I reaction by dissolving smectite through reduction of structural Fe(III) at room temperature and 1 atmosphere within 14 days. This reaction typically requires conditions of 300 degrees to 350 degrees C, 100 megapascals, and 4 to 5 months in the absence of microbial activity. These results challenge the conventional concept of the S-I reaction and of reaction kinetic models.

Online monitoring of a photocatalytic reaction by real-time high resolution FlowNMR spectroscopy.

PubMed

Hall, Andrew M R; Broomfield-Tagg, Rachael; Camilleri, Matthew; Carbery, David R; Codina, Anna; Whittaker, David T E; Coombes, Steven; Lowe, John P; Hintermair, Ulrich

2017-12-19

We demonstrate how FlowNMR spectroscopy can readily be applied to investigate photochemical reactions that require sustained input of light and air to yield mechanistic insight under realistic conditions. The Eosin Y mediated photo-oxidation of N-allylbenzylamine is shown to produce imines as primary reaction products from which undesired aldehydes form after longer reaction times. Facile variation of reaction conditions during the reaction in flow allows for probe experiments that give information about the mode of action of the photocatalyst.

Social support attenuates presyncopal reactions to blood donation.

PubMed

Hanson, Sarah A; France, Christopher R

2009-05-01

The experience of unpleasant blood donation reactions (e.g., dizziness, nausea, and fainting) has been linked to negative attitudes about donation and decreased likelihood of repeat donation. Consequently, interventions to reduce the adverse effects of blood donation are important and likely to increase donor retention. Based on laboratory studies suggesting that social support attenuates both physical and psychological responses to stress, the present study hypothesized that the presence of a supportive person during the donation process may help reduce reactions. A final sample of 65 men and women with fewer than three prior donations was randomly assigned to either donate blood as usual or donate with a supportive research assistant. Donors in the support condition were accompanied throughout the donation process by a female research assistant who provided encouragement, made reassuring remarks, and engaged in small talk. Donors in both conditions completed a series of questions to assess anxiety, experience of prefaint reactions, and willingness to provide a future donation. Compared to standard donation controls, donors in the social support condition reported fewer prefaint reactions (F(1,61) = 9.15, p = 0.004, eta(2)= 0.13) and greater likelihood of donating again within the next year (Z =-1.70, p < 0.05, one-tailed). Relatively novice donors report reduced reactions to blood donation when accompanied by a supportive individual, suggesting that social support may be a simple strategy to enhance the donation experience and possibly increase donor retention.

Hemoglobin redox reactions and red blood cell aging.

PubMed

Rifkind, Joseph M; Nagababu, Enika

2013-06-10

The physiological mechanism(s) for recognition and removal of red blood cells (RBCs) from circulation after 120 days of its lifespan is not fully understood. Many of the processes thought to be associated with the removal of RBCs involve oxidative stress. We have focused on hemoglobin (Hb) redox reactions, which is the major source of RBC oxidative stress. The importance of Hb redox reactions have been shown to originate in large parts from the continuous slow autoxidation of Hb producing superoxide and its dramatic increase under hypoxic conditions. In addition, oxidative stress has been shown to be associated with redox reactions that originate from Hb reactions with nitrite and nitric oxide (NO) and the resultant formation of highly toxic peroxynitrite when NO reacts with superoxide released during Hb autoxidation. The interaction of Hb, particularly under hypoxic conditions with band 3 of the RBC membrane is critical for the generating the RBC membrane changes that trigger the removal of cells from circulation. These changes include exposure of antigenic sites, increased calcium leakage into the RBC, and the resultant leakage of potassium out of the RBC causing cell shrinkage and impaired deformability. The need to understand the oxidative damage to specific membrane proteins that result from redox reactions occurring when Hb is bound to the membrane. Proteomic studies that can pinpoint the specific proteins damaged under different conditions will help elucidate the cellular aging processes that result in cells being removed from circulation.

Astrophysical Nuclear Reaction Rates in the Dense Metallic Environments

NASA Astrophysics Data System (ADS)

Kilic, Ali Ihsan

2017-09-01

Nuclear reaction rates can be enhanced by many orders of magnitude in dense and relatively cold astrophysical plasmas such as in white dwarfs, brown dwarfs, and giant planets. Similar conditions are also present in supernova explosions where the ignition conditions are vital for cosmological models. White dwarfs are compact objects that have both extremely high interior densities and very strong local magnetic fields. For the first time, a new formula has been developed to explain cross section and reaction rate quantities for light elements that includes not only the nuclear component but also the material dependence, magnetic field, and crystal structure dependency in dense metallic environments. I will present the impact of the developed formula on the cross section and reaction rates for light elements. This could have possible technological applications in energy production using nuclear fusion reactions.

Novel multicomponent reaction for the combinatorial synthesis of 2-imidazolines.

PubMed

Bon, Robin S; Hong, Chongen; Bouma, Marinus J; Schmitz, Rob F; de Kanter, Frans J J; Lutz, Martin; Spek, Anthony L; Orru, Romano V A

2003-10-02

[reaction: see text] The three-component condensation between an amine, an aldehyde, and an alpha-acidic isocyanide efficiently provides substituted 2-imidazolines in a one-pot reaction under mild conditions.

Quantum dynamics of the Eley-Rideal hydrogen formation reaction on graphite at typical interstellar cloud conditions.

PubMed

Casolo, Simone; Martinazzo, Rocco; Bonfanti, Matteo; Tantardini, Gian Franco

2009-12-31

Eley-Rideal formation of hydrogen molecules on graphite, as well as competing collision induced processes, are investigated quantum dynamically at typical interstellar cloud conditions, focusing in particular on gas-phase temperatures below 100 K, where much of the chemistry of the so-called diffuse clouds takes place on the surface of bare carbonaceous dust grains. Collisions of gas-phase hydrogen atoms with both chemisorbed and physisorbed species are considered using available potential energy surfaces (Sha et al., J. Chem. Phys.2002 116, 7158), and state-to-state, energy-resolved cross sections are computed for a number of initial vibrational states of the hydrogen atoms bound to the surface. Results show that (i) product molecules are internally hot in both cases, with vibrational distributions sharply peaked around few (one or two) vibrational levels, and (ii) cross sections for chemisorbed species are 2-3x smaller than those for physisorbed ones. In particular, we find that H(2) formation cross sections out of chemically bound species decrease steadily when the temperature drops below approximately 1000 K, and this is likely due to a quantum reflection phenomenon. This suggests that such Eley-Rideal reaction is all but efficient in the relevant gas-phase temperature range, even when gas-phase H atoms happen to chemisorb barrierless to the surface as observed, e.g., for forming so-called para dimers. Comparison with results from classical trajectory calculations highlights the need of a quantum description of the dynamics in the astrophysically relevant energy range, whereas preliminary results of an extensive first-principles investigation of the reaction energetics reveal the importance of the adopted substrate model.

Copper-catalyzed oxidative Heck reactions between alkyltrifluoroborates and vinyl arenes.

PubMed

Liwosz, Timothy W; Chemler, Sherry R

2013-06-21

We report herein that potassium alkyltrifluoroborates can be utilized in oxidative Heck-type reactions with vinyl arenes. The reaction is catalyzed by a Cu(OTf)2/1,10-phenanthroline with MnO2 as the stoichiometric oxidant. In addition to the alkyl Heck, amination, esterification, and dimerization reactions of alkyltrifluoroborates are demonstrated under analogous reaction conditions. Evidence for an alkyl radical intermediate is presented.

Piper-betle-shaped nano-S-catalyzed synthesis of 1-amidoalkyl-2-naphthols under solvent-free reaction condition: a greener "nanoparticle-catalyzed organic synthesis enhancement" approach.

PubMed

Das, Vijay K; Borah, Madhurjya; Thakur, Ashim J

2013-04-05

Nano-S prepared by an annealing process showed excellent catalytic activity for the synthesis of 1-amidoalkyl-2-naphthols under solvent-free reaction condition at 50 °C. The catalyst could be reused up to the fifth cycle without loss in its action. The green-ness of the present protocol was also measured using green metrics drawing its superiority.

FORMATE—PYRUVATE EXCHANGE REACTION IN STREPTOCOCCUS FAECALIS II.

PubMed Central

Oster, M. O.; Wood, N. P.

1964-01-01

Oster, M. O. (A. & M. College of Texas, College Station), and N. P. Wood. Formate-pyruvate exchange reaction in Streptococcus faecalis. II. Reaction conditions for cell extracts. J. Bacteriol. 87:104–113. 1964.—In contrast to intact cells of Streptococcus faecalis, no stimulation of the formate-pyruvate exchange reaction was observed in cell extracts when yeast extract was added to the reaction mixture. A heated extract of Micrococcus lactilyticus, vitamin K5, ferrous sulfate, and ferrous ammonium sulfate stimulated an active exchange by protecting the system from oxygen. Tetrahydrofolate, 2,3-dimercaptopropanol, and sodium sulfide provided partial protection, whereas ascorbate, glutathione, sodium hydrosulfite, ammonium sulfide, and sodium bisulfite gave insufficient protection or were inhibitory. Oxidation-reduction (O-R) indicators were not inhibitory and were used to estimate the O-R potentials of reaction mixtures. A potential at least as negative as −125 mv was estimated to be necessary to preserve or initiate formate-pyruvate exchange activity. The reaction operated over a narrow pH range when strict anaerobic conditions were not maintained but, when the system was suitably poised, the pH range was broader. The influence of high phosphate concentrations was less under strictly anaerobic conditions, and orthophosphate could be replaced by small amounts of pyrophosphate. Effect of temperature, time, and amount of extract is presented. Addition of reduced benzyl viologen and hydrogen-saturated palladium in the buffer during 8 hr of dialysis prevented inactivation of extracts. Recovery of activity could be obtained after ammonium sulfate treatment when a combination of palladium chloride, neutral red, and hydrogen bubbling were used. PMID:14102842

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…

Modeling of uncertainties in biochemical reactions.

PubMed

Mišković, Ljubiša; Hatzimanikatis, Vassily

2011-02-01

Mathematical modeling is an indispensable tool for research and development in biotechnology and bioengineering. The formulation of kinetic models of biochemical networks depends on knowledge of the kinetic properties of the enzymes of the individual reactions. However, kinetic data acquired from experimental observations bring along uncertainties due to various experimental conditions and measurement methods. In this contribution, we propose a novel way to model the uncertainty in the enzyme kinetics and to predict quantitatively the responses of metabolic reactions to the changes in enzyme activities under uncertainty. The proposed methodology accounts explicitly for mechanistic properties of enzymes and physico-chemical and thermodynamic constraints, and is based on formalism from systems theory and metabolic control analysis. We achieve this by observing that kinetic responses of metabolic reactions depend: (i) on the distribution of the enzymes among their free form and all reactive states; (ii) on the equilibrium displacements of the overall reaction and that of the individual enzymatic steps; and (iii) on the net fluxes through the enzyme. Relying on this observation, we develop a novel, efficient Monte Carlo sampling procedure to generate all states within a metabolic reaction that satisfy imposed constrains. Thus, we derive the statistics of the expected responses of the metabolic reactions to changes in enzyme levels and activities, in the levels of metabolites, and in the values of the kinetic parameters. We present aspects of the proposed framework through an example of the fundamental three-step reversible enzymatic reaction mechanism. We demonstrate that the equilibrium displacements of the individual enzymatic steps have an important influence on kinetic responses of the enzyme. Furthermore, we derive the conditions that must be satisfied by a reversible three-step enzymatic reaction operating far away from the equilibrium in order to respond to

Thermally multiplexed polymerase chain reaction.

PubMed

Phaneuf, Christopher R; Pak, Nikita; Saunders, D Curtis; Holst, Gregory L; Birjiniuk, Joav; Nagpal, Nikita; Culpepper, Stephen; Popler, Emily; Shane, Andi L; Jerris, Robert; Forest, Craig R

2015-07-01

Amplification of multiple unique genetic targets using the polymerase chain reaction (PCR) is commonly required in molecular biology laboratories. Such reactions are typically performed either serially or by multiplex PCR. Serial reactions are time consuming, and multiplex PCR, while powerful and widely used, can be prone to amplification bias, PCR drift, and primer-primer interactions. We present a new thermocycling method, termed thermal multiplexing, in which a single heat source is uniformly distributed and selectively modulated for independent temperature control of an array of PCR reactions. Thermal multiplexing allows amplification of multiple targets simultaneously-each reaction segregated and performed at optimal conditions. We demonstrate the method using a microfluidic system consisting of an infrared laser thermocycler, a polymer microchip featuring 1 μl, oil-encapsulated reactions, and closed-loop pulse-width modulation control. Heat transfer modeling is used to characterize thermal performance limitations of the system. We validate the model and perform two reactions simultaneously with widely varying annealing temperatures (48 °C and 68 °C), demonstrating excellent amplification. In addition, to demonstrate microfluidic infrared PCR using clinical specimens, we successfully amplified and detected both influenza A and B from human nasopharyngeal swabs. Thermal multiplexing is scalable and applicable to challenges such as pathogen detection where patients presenting non-specific symptoms need to be efficiently screened across a viral or bacterial panel.

Youth’s Reactions to Disasters and the Factors That Influence Their Response

PubMed Central

Pfefferbaum, Betty; Houston, J. Brian; North, Carol S.; Regens, James L.

2009-01-01

Youth’s reactions to disasters include stress reactions, posttraumatic stress disorder (PTSD), and comorbid conditions. A number of factors contribute to outcome including characteristics of the event; the nature of the youth’s exposure; and individual, family, and social predictors. Demographic features may be less important than exposure and other individual variables like preexisting conditions and exposure to other trauma. While youth’s disaster reactions reflect their developmental status and thus may differ from those of adults, their reactions generally parallel those of their parents in degree. Family factors that appear to influence youth’s reactions include parental reactions and the quality of interactions within the family. Social factors have not been well examined. We describe these outcomes and predictors to prepare professionals who may work with youth in post-disaster situations. PMID:19953191

Characterization of plastic deformation and chemical reaction in titanium-polytetrafluoroethylene mixture

NASA Astrophysics Data System (ADS)

Davis, Jeffery Jon

1998-09-01

The subject of this dissertation is the deformation process of a single metal - polymer system (titanium - polytetrafluoroethylene) and how this process leads to initiation of chemical reaction. Several different kinds of experiments were performed to characterize the behavior of this material to shock and impact. These mechanical conditions induce a rapid plastic deformation of the sample. All of the samples tested had an initial porosity which increased the plastic flow condition. It is currently believed that during the deformation process two important conditions occur: removal of the oxide layer from the metal and decomposition of the polymer. These conditions allow for rapid chemical reaction. The research from this dissertation has provided insight into the complex behavior of plastic deformation and chemical reactions in titanium - polytetrafluoroethylene (PTFE, Teflon). A hydrodynamic computational code was used to model the plastic flow for correlation with the results from the experiments. The results from this work are being used to develop an ignition and growth model for metal/polymer systems. Three sets of experiments were used to examine deformation of the 80% Ti and 20% Teflon materials: drop- weight, gas gun, and split-Hopkinson pressure bar. Recovery studies included post shot analysis of the samples using x-ray diffraction. Lagrangian hydrocode DYNA2D modeling of the drop-weight tests was performed for comparison with experiments. One of the reactions know to occur is Ti + C → TiC (s) which results in an exothermic release. However, the believed initial reactions occur between Ti and fluorine which produces TixFy gases. The thermochemical code CHEETAH was used to investigate the detonation products and concentrations possible during Ti - Teflon reaction. CHEETAH shows that the Ti - fluorine reactions are thermodynamically favorable. This research represents the most comprehensive to date study of deformation induced chemical reaction in metal/polymers.

Characterization of shock-dependent reaction rates in an aluminum/perfluoropolyether pyrolant

NASA Astrophysics Data System (ADS)

Wilson, Dennis; Granier, John; Johnson, Richard; Littrell, Donald

2017-01-01

Energetic formulations of perfluoropolyether (PFPE) and aluminum are highly non-ideal. They release energy via a fast self-oxidized combustion wave rather than a true self-sustaining detonation. Unlike high explosives, the reactions are shock dependent and can be overdriven to control energy release rate. Reaction rate experiments show that the velocity can vary from 1.25 to 3 km/s. This paper examines the effect of the initial shock conditions upon the reaction rate of the explosive. The following conditions were varied in a series of reaction rate experiments: the high explosive booster mass and geometry; shock attenuation; confinement; and rate stick diameter and length. Several experiments designed to isolate and quantify these dependencies are described and summarized.

A dual-process model of reactions to perceived stigma.

PubMed

Pryor, John B; Reeder, Glenn D; Yeadon, Christopher; Hesson-McLnnis, Matthew

2004-10-01

The authors propose a theoretical model of individual psychological reactions to perceived stigma. This model suggests that 2 psychological systems may be involved in reactions to stigma across a variety of social contexts. One system is primarily reflexive, or associative, whereas the other is rule based, or reflective. This model assumes a temporal pattern of reactions to the stigmatized, such that initial reactions are governed by the reflexive system, whereas subsequent reactions or "adjustments" are governed by the rule-based system. Support for this model was found in 2 studies. Both studies examined participants' moment-by-moment approach-avoidance reactions to the stigmatized. The 1st involved participants' reactions to persons with HIV/AIDS, and the 2nd, participants' reactions to 15 different stigmatizing conditions. (c) 2004 APA, all rights reserved

The reaction mechanism with free energy barriers at constant potentials for the oxygen evolution reaction at the IrO 2 (110) surface

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

Ping, Yuan; Nielsen, Robert J.; Goddard, William A.

How to efficiently oxidize H 2O to O 2 (oxygen evolution reaction, OER) in photoelectrochemical cells (PEC) is a great challenge due to its complex charge transfer process, high overpotential, and corrosion. So far no OER mechanism has been fully explained atomistically with both thermodynamic and kinetics. IrO 2 is the only known OER catalyst with both high catalytic activity and stability in acidic conditions. This is important because PEC experiments often operate at extreme pH conditions. In this work, we performed first-principles calculations integrated with implicit solvation at constant potentials to examine the detailed atomistic reaction mechanism of OERmore » at the IrO 2 (110) surface. We determined the surface phase diagram, explored the possible reaction pathways including kinetic barriers, and computed reaction rates based on the microkinetic models. Furthermore, this allowed us to resolve several long-standing puzzles about the atomistic OER mechanism.« less

The reaction mechanism with free energy barriers at constant potentials for the oxygen evolution reaction at the IrO 2 (110) surface

DOE PAGES

Ping, Yuan; Nielsen, Robert J.; Goddard, William A.

2016-12-09

How to efficiently oxidize H 2O to O 2 (oxygen evolution reaction, OER) in photoelectrochemical cells (PEC) is a great challenge due to its complex charge transfer process, high overpotential, and corrosion. So far no OER mechanism has been fully explained atomistically with both thermodynamic and kinetics. IrO 2 is the only known OER catalyst with both high catalytic activity and stability in acidic conditions. This is important because PEC experiments often operate at extreme pH conditions. In this work, we performed first-principles calculations integrated with implicit solvation at constant potentials to examine the detailed atomistic reaction mechanism of OERmore » at the IrO 2 (110) surface. We determined the surface phase diagram, explored the possible reaction pathways including kinetic barriers, and computed reaction rates based on the microkinetic models. Furthermore, this allowed us to resolve several long-standing puzzles about the atomistic OER mechanism.« less

Design of experiments for zeroth and first-order reaction rates.

PubMed

Amo-Salas, Mariano; Martín-Martín, Raúl; Rodríguez-Aragón, Licesio J

2014-09-01

This work presents optimum designs for reaction rates experiments. In these experiments, time at which observations are to be made and temperatures at which reactions are to be run need to be designed. Observations are performed along time under isothermal conditions. Each experiment needs a fixed temperature and so the reaction can be measured at the designed times. For these observations under isothermal conditions over the same reaction a correlation structure has been considered. D-optimum designs are the aim of our work for zeroth and first-order reaction rates. Temperatures for the isothermal experiments and observation times, to obtain the most accurate estimates of the unknown parameters, are provided in these designs. D-optimum designs for a single observation in each isothermal experiment or for several correlated observations have been obtained. Robustness of the optimum designs for ranges of the correlation parameter and comparisons of the information gathered by different designs are also shown. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic Intermolecular Pauson - Khand Reactions in Supercritical Ethylene.

PubMed

Jeong; Hwang

2000-02-01

Ethylene is not only a substrate, but also a solvent: Catalytic intermolecular Pauson - Khand reactions of terminal alkynes were carried out in supercritical ethylene to provide 2-substituted cyclopentenones in moderate to high yields [Eq. (1)]. Under these conditions, even a low pressure of CO (5 atm) is sufficient for the reaction to take place.

14 CFR 25.485 - Side load conditions.

Code of Federal Regulations, 2010 CFR

2010-01-01

... accordance with figure 5 of appendix A. (b) Side loads of 0.8 of the vertical reaction (on one side) acting inward and 0.6 of the vertical reaction (on the other side) acting outward must be combined with one-half of the maximum vertical ground reactions obtained in the level landing conditions. These loads are...

14 CFR 25.485 - Side load conditions.

Code of Federal Regulations, 2011 CFR

2011-01-01

... accordance with figure 5 of appendix A. (b) Side loads of 0.8 of the vertical reaction (on one side) acting inward and 0.6 of the vertical reaction (on the other side) acting outward must be combined with one-half of the maximum vertical ground reactions obtained in the level landing conditions. These loads are...

Plasmon-driven sequential chemical reactions in an aqueous environment.

PubMed

Zhang, Xin; Wang, Peijie; Zhang, Zhenglong; Fang, Yurui; Sun, Mengtao

2014-06-24

Plasmon-driven sequential chemical reactions were successfully realized in an aqueous environment. In an electrochemical environment, sequential chemical reactions were driven by an applied potential and laser irradiation. Furthermore, the rate of the chemical reaction was controlled via pH, which provides indirect evidence that the hot electrons generated from plasmon decay play an important role in plasmon-driven chemical reactions. In acidic conditions, the hot electrons were captured by the abundant H(+) in the aqueous environment, which prevented the chemical reaction. The developed plasmon-driven chemical reactions in an aqueous environment will significantly expand the applications of plasmon chemistry and may provide a promising avenue for green chemistry using plasmon catalysis in aqueous environments under irradiation by sunlight.

Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons

NASA Astrophysics Data System (ADS)

Külah, Elçin; Marot, Laurent; Steiner, Roland; Romanyuk, Andriy; Jung, Thomas A.; Wäckerlin, Aneliia; Meyer, Ernst

2017-03-01

Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C18H12) on a Gd2O3. Our study evidences a novel effect - oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level.

Horseradish-Peroxidase-Catalyzed Tyrosine Click Reaction.

PubMed

Sato, Shinichi; Nakamura, Kosuke; Nakamura, Hiroyuki

2017-03-02

The efficiency of protein chemical modification on tyrosine residues with N-methylluminol derivatives was drastically improved by using horseradish peroxidase (HRP). In the previous method, based on the use of hemin and H 2 O 2 , oxidative side reactions such as cysteine oxidation were problematic for functionalization of proteins selectively on tyrosine residues. Oxidative activation of N-methylluminol derivatives with a minimum amount of H 2 O 2 prevented the occurrence of oxidative side reactions under HRP-catalyzed conditions. As probes for HRP-catalyzed protein modification, N-methylluminol derivatives showed much higher efficiency than tyramide without inducing oligomerization of probe molecules. Tyrosine modification also proceeded in the presence of β-nicotinamide adenine dinucleotide (NADH, H 2 O 2 -free conditions). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamics of random reaction networks.

PubMed

Fischer, Jakob; Kleidon, Axel; Dittrich, Peter

2015-01-01

Reaction networks are useful for analyzing reaction systems occurring in chemistry, systems biology, or Earth system science. Despite the importance of thermodynamic disequilibrium for many of those systems, the general thermodynamic properties of reaction networks are poorly understood. To circumvent the problem of sparse thermodynamic data, we generate artificial reaction networks and investigate their non-equilibrium steady state for various boundary fluxes. We generate linear and nonlinear networks using four different complex network models (Erdős-Rényi, Barabási-Albert, Watts-Strogatz, Pan-Sinha) and compare their topological properties with real reaction networks. For similar boundary conditions the steady state flow through the linear networks is about one order of magnitude higher than the flow through comparable nonlinear networks. In all networks, the flow decreases with the distance between the inflow and outflow boundary species, with Watts-Strogatz networks showing a significantly smaller slope compared to the three other network types. The distribution of entropy production of the individual reactions inside the network follows a power law in the intermediate region with an exponent of circa -1.5 for linear and -1.66 for nonlinear networks. An elevated entropy production rate is found in reactions associated with weakly connected species. This effect is stronger in nonlinear networks than in the linear ones. Increasing the flow through the nonlinear networks also increases the number of cycles and leads to a narrower distribution of chemical potentials. We conclude that the relation between distribution of dissipation, network topology and strength of disequilibrium is nontrivial and can be studied systematically by artificial reaction networks.

Microscale imaging and identification of Fe speciation and distribution during fluid-mineral reactions under highly reducing conditions.

PubMed

Mayhew, L E; Webb, S M; Templeton, A S

2011-05-15

The oxidation state, speciation, and distribution of Fe are critical determinants of Fe reactivity in natural and engineered environments. However, it is challenging to follow dynamic changes in Fe speciation in environmental systems during progressive fluid-mineral interactions. Two common geological and aquifer materials-basalt and Fe(III) oxides-were incubated with saline fluids at 55 °C under highly reducing conditions maintained by the presence of Fe(0). We tracked changes in Fe speciation after 48 h (incipient water-rock reaction) and 10 months (extensive water-rock interaction) using synchrotron-radiation μXRF maps collected at multiple energies (ME) within the Fe K-edge. Immediate PCA analysis of the ME maps was used to optimize μXANES analyses; in turn, refitting the ME maps with end-member XANES spectra enabled us to detect and spatially resolve the entire variety of Fe-phases present in the system. After 48 h, we successfully identified and mapped the major Fe-bearing components of our samples (Fe(III) oxides, basalt, and rare olivine), as well as small quantities of incipient brucite associated with olivine. After 10 months, the Fe(III)-oxides remained stable in the presence of Fe(0), whereas significant alteration of basalt to minnesotaite and chlinochlore had occurred, providing new insights into heterogeneous Fe speciation in complex geological media under highly reducing conditions.

Nitropyrroles, Diels-Alder reactions assisted by microwave irradiation and solvent effect. An experimental and theoretical study

NASA Astrophysics Data System (ADS)

Mancini, Pedro M. E.; Kneeteman, María N.; Cainelli, Mauro; Ormachea, Carla M.; Domingo, Luis R.

2017-11-01

The behaviors of N-tosylnitropyrroles acting as electrophilic dienophiles in polar Diels-Alder reactions joint to different dienes of increeased nucleophilicity are analyzed. The reactions were developed under microwave irradiation using toluene or protic ionic liquids (PILs) as solvents and in free solvent conditions. In all the cases explored we observed good yields in short reaction times. For these reactions, the free solvent condition and the use of protic ionic liquids as solvents offer similar results. However, the free solvent conditions favor environmental sustainability. The role of PILs in these polar Diels-Alder reactions has been theoretically studied within the Molecular Electron Density Theory.

Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product

NASA Technical Reports Server (NTRS)

David, Dennis D.; Dee, Louis A.; Beeson, Harold D.

1997-01-01

Fuel-oxidizer reaction product (FORP), the product of incomplete reaction of monomethylhydrazine and nitrogen tetroxide propellants prepared under laboratory conditions and from firings of Shuttle Reaction Control System thrusters, has been characterized by chemical and thermal analysis. The composition of FORP is variable but falls within a limited range of compositions that depend on three factors: the fuel-oxidizer ratio at the time of formation; whether the composition of the post-formation atmosphere is reducing or oxidizing; and the reaction or post-reaction temperature. A typical composition contains methylhydrazinium nitrate, ammonium nitrate, methylammonium nitrate, and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. Thermal decomposition reactions of the FORP compositions used in this study were unremarkable. Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid monomethylhydrazine and liquid nitrogen tetroxide in a confined space. These tests demonstrated that monomethylhydrazine, methylhydrazinium nitrate, ammonium nitrate, or Inconel corrosion products can induce a mixture of monomethylhydrazine and nitrogen tetroxide to produce component-damaging energies. Damaging events required FORP or metal salts to be present at the initial mixing of monomethylhydrazine and nitrogen tetroxide.

Perspective: Chemical reactions in ionic liquids monitored through the gas (vacuum)/liquid interface.

PubMed

Maier, F; Niedermaier, I; Steinrück, H-P

2017-05-07

This perspective analyzes the potential of X-ray photoelectron spectroscopy under ultrahigh vacuum (UHV) conditions to follow chemical reactions in ionic liquids in situ. Traditionally, only reactions occurring on solid surfaces were investigated by X-ray photoelectron spectroscopy (XPS) in situ. This was due to the high vapor pressures of common liquids or solvents, which are not compatible with the required UHV conditions. It was only recently realized that the situation is very different when studying reactions in Ionic Liquids (ILs), which have an inherently low vapor pressure, and first studies have been performed within the last years. Compared to classical spectroscopy techniques used to monitor chemical reactions, the advantage of XPS is that through the analysis of their core levels all relevant elements can be quantified and their chemical state can be analyzed under well-defined (ultraclean) conditions. In this perspective, we cover six very different reactions which occur in the IL, with the IL, or at an IL/support interface, demonstrating the outstanding potential of in situ XPS to gain insights into liquid phase reactions in the near-surface region.

Growth of enstatite and enstatite-forsterite reaction rims under wet conditions during isostatic annealing and triaxial deformation

NASA Astrophysics Data System (ADS)

Helpa, Vanessa; Rybacki, Erik; Dresen, Georg

2017-04-01

To investigate the influence of differential stress and microstructure on reaction rates, we studied experimentally enstatite-forsterite double rim formation in between periclase and quartz according to the reaction MgO +

Solid-supported nitroso hetero Diels-Alder reactions. 1. Acylnitroso dienophiles: scope and limitations.

PubMed

Krchnák, Viktor; Moellmann, Ute; Dahse, Hans-Martin; Miller, Marvin J

2008-01-01

Polymer-supported acylnitroso dienophiles were prepared and used in hetero Diels-Alder (HDA) reactions with a variety of dienes. The transient acylnitroso dienophiles were prepared in situ from immobilized hydroxamates, which were attached to solid supports via several linkers each cleavable by different cleavage reagents, and served for the synthesis of both N-unsubstituted and N-derivatized HDA adducts. Model compounds were used to (i) optimize reaction conditions for solid-supported HDA reactions, (ii) evaluate the outcome of the reactions with various dienes, (iii) compare relative reactivities of dienes, and (iv) assess the stability of HDA adducts toward cleavage conditions typically used in solid-phase syntheses. Cleaved products were submitted to biological assays, and the results are reported. The accompanying paper, focused on complementary arylnitroso HDA reactions, includes a comparison of both HDA reactions.

Plasmon-driven sequential chemical reactions in an aqueous environment

PubMed Central

Zhang, Xin; Wang, Peijie; Zhang, Zhenglong; Fang, Yurui; Sun, Mengtao

2014-01-01

Plasmon-driven sequential chemical reactions were successfully realized in an aqueous environment. In an electrochemical environment, sequential chemical reactions were driven by an applied potential and laser irradiation. Furthermore, the rate of the chemical reaction was controlled via pH, which provides indirect evidence that the hot electrons generated from plasmon decay play an important role in plasmon-driven chemical reactions. In acidic conditions, the hot electrons were captured by the abundant H+ in the aqueous environment, which prevented the chemical reaction. The developed plasmon-driven chemical reactions in an aqueous environment will significantly expand the applications of plasmon chemistry and may provide a promising avenue for green chemistry using plasmon catalysis in aqueous environments under irradiation by sunlight. PMID:24958029

Enantioselective aldol reactions with masked fluoroacetates

NASA Astrophysics Data System (ADS)

Saadi, Jakub; Wennemers, Helma

2016-03-01

Despite the growing importance of organofluorines as pharmaceuticals and agrochemicals, the stereoselective introduction of fluorine into many prominent classes of natural products and chemotherapeutic agents is difficult. One long-standing unsolved challenge is the enantioselective aldol reaction of fluoroacetate to enable access to fluorinated analogues of medicinally relevant acetate-derived compounds, such as polyketides and statins. Herein we present fluoromalonic acid halfthioesters as biomimetic surrogates of fluoroacetate and demonstrate their use in highly stereoselective aldol reactions that proceed under mild organocatalytic conditions. We also show that the methodology can be extended to formal aldol reactions with fluoroacetaldehyde and consecutive aldol reactions. The synthetic utility of the fluorinated aldol products is illustrated by the synthesis of a fluorinated derivative of the top-selling drug atorvastatin. The results show the prospects of the method for the enantioselective introduction of fluoroacetate to access a wide variety of highly functionalized fluorinated compounds.

A Petri net approach to the study of persistence in chemical reaction networks.

PubMed

Angeli, David; De Leenheer, Patrick; Sontag, Eduardo D

2007-12-01

Persistence is the property, for differential equations in R(n), that solutions starting in the positive orthant do not approach the boundary of the orthant. For chemical reactions and population models, this translates into the non-extinction property: provided that every species is present at the start of the reaction, no species will tend to be eliminated in the course of the reaction. This paper provides checkable conditions for persistence of chemical species in reaction networks, using concepts and tools from Petri net theory, and verifies these conditions on various systems which arise in the modeling of cell signaling pathways.

Cocondensation of urea with methylolphenols in acidic conditions

Treesearch

Bunchiro Tomita; Chung-Yun Hse

1992-01-01

The reactions of urea with methylolphenols under acidic conditions were investigated using 2- and 4-hydroxybenzyl alcohol and crude 2,4,6-trimethylophenol as model compounds. The reaction products were analyzed with 13C-NMR spectroscopy and GPC. From the reaction of urea with 4-hydroxybenzyl alcohol, the formations of 4-hydroxybenzylurea,

Transglycosylation reactions, a main mechanism of phenolics incorporation in coffee melanoidins: Inhibition by Maillard reaction.

PubMed

Moreira, Ana S P; Nunes, Fernando M; Simões, Cristiana; Maciel, Elisabete; Domingues, Pedro; Domingues, M Rosário M; Coimbra, Manuel A

2017-07-15

Under roasting conditions, polysaccharides depolymerize and also are able to polymerize, forming new polymers through non-enzymatic transglycosylation reactions (TGRs). TGRs can also occur between carbohydrates and aglycones, such as the phenolic compounds present in daily consumed foods like coffee. In this study, glycosidically-linked phenolic compounds were quantified in coffee melanoidins, the polymeric nitrogenous brown-colored compounds formed during roasting, defined as end-products of Maillard reaction. One third of the phenolics present were in glycosidically-linked form. In addition, the roasting of solid-state mixtures mimicking coffee beans composition allowed the conclusion that proteins play a regulatory role in TGRs extension and, consequently, modulate melanoidins composition. Overall, the results obtained showed that TGRs are a main mechanism of phenolics incorporation in melanoidins and are inhibited by amino groups through Maillard reaction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Treatment of arsenic in acid wastewater and river sediment by Fe@Fe2O3 nanobunches: The effect of environmental conditions and reaction mechanism.

PubMed

Tang, Lin; Feng, Haopeng; Tang, Jing; Zeng, Guangming; Deng, Yaocheng; Wang, Jiajia; Liu, Yani; Zhou, Yaoyu

2017-06-15

High concentration of arsenic in acid wastewater and polluted river sediment caused by metallurgical industry has presented a great environmental challenge for decades. Nanoscale zero valent iron (nZVI) can detoxify arsenic-bearing wastewater and groundwater, but the low adsorption capacity and rapid passivation restrict its large-scale application. This study proposed a highly efficient arsenic treatment nanotechnology, using the core-shell Fe@Fe 2 O 3 nanobunches (NBZI) for removal of arsenic in acid wastewater with cyclic stability and transformation of arsenic speciation in sediment. The adsorption capacity of As(III) by NBZI was 60 times as high as that of nanoscale zero valent iron (nZVI) at neutral pH. Characterization of the prepared materials after reaction revealed that the contents of As(III) and As(V) were 65% and 35% under aerobic conditions, respectively, which is the evidence of oxidation included in the reaction process apart from adsorption and co-precipitation. The presence of oxygen was proved to improve the adsorption ability of the prepared NBZI towards As(III) with the removal efficiency increasing from 68% to 92%. In order to further enhance the performance of NBZI-2 in the absence of oxygen, a new Fenton-Like system of NBZI/H 2 O 2 to remove arsenic under the anoxic condition was also proposed. Furthermore, the removal efficiency of arsenic in acid wastewater remained to be 78% after 9 times of cycling. Meanwhile, most of the mobile fraction of arsenic in river sediment was transformed into residues after NBZI treatment for 20 days. The reaction mechanism between NBZI and arsenic was discussed in detail at last, indicating great potential of NBZI for the treatment of arsenic in wastewater and sediment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Presidential Green Chemistry Challenge: 2008 Greener Reaction Conditions Award

EPA Pesticide Factsheets

Presidential Green Chemistry Challenge 2008 award winner, Nalco Company, developed 3D TRASAR technology to monitor the condition of cooling water continuously and add chemicals only when needed, saving water and energy.

Delta-9-tetrahydrocannabinol and cannabidiol, but not ondansetron, interfere with conditioned retching reactions elicited by a lithium-paired context in Suncus murinus: An animal model of anticipatory nausea and vomiting.

PubMed

Parker, Linda A; Kwiatkowska, Magdalena; Mechoulam, Raphael

2006-01-30

Chemotherapy patients report not only acute nausea and vomiting during the treatment itself, but also report anticipatory nausea and vomiting upon re-exposure to the cues associated with the treatment. We present a model of anticipatory nausea based on the emetic reactions of the Suncus murinus (musk shrew). Following three pairings of a novel distinctive contextual cue with the emetic effects of an injection of lithium chloride, the context acquired the potential to elicit conditioned retching in the absence of the toxin. The expression of this conditioned retching reaction was completely suppressed by pretreatment with each of the principal cannabinoids found in marijuana, Delta(9)-tetrahydrocannabinol or cannabidiol, at a dose that did not suppress general activity. On the other hand, pretreatment with a dose of ondansetron (a 5-HT(3) antagonist) that interferes with acute vomiting in this species, did not suppress the expression of conditioned retching during re-exposure to the lithium-paired context. These results support anecdotal claims that marijuana, but not ondansetron, may suppress the expression of anticipatory nausea.

Thermodynamics of Random Reaction Networks

PubMed Central

Fischer, Jakob; Kleidon, Axel; Dittrich, Peter

2015-01-01

Reaction networks are useful for analyzing reaction systems occurring in chemistry, systems biology, or Earth system science. Despite the importance of thermodynamic disequilibrium for many of those systems, the general thermodynamic properties of reaction networks are poorly understood. To circumvent the problem of sparse thermodynamic data, we generate artificial reaction networks and investigate their non-equilibrium steady state for various boundary fluxes. We generate linear and nonlinear networks using four different complex network models (Erdős-Rényi, Barabási-Albert, Watts-Strogatz, Pan-Sinha) and compare their topological properties with real reaction networks. For similar boundary conditions the steady state flow through the linear networks is about one order of magnitude higher than the flow through comparable nonlinear networks. In all networks, the flow decreases with the distance between the inflow and outflow boundary species, with Watts-Strogatz networks showing a significantly smaller slope compared to the three other network types. The distribution of entropy production of the individual reactions inside the network follows a power law in the intermediate region with an exponent of circa −1.5 for linear and −1.66 for nonlinear networks. An elevated entropy production rate is found in reactions associated with weakly connected species. This effect is stronger in nonlinear networks than in the linear ones. Increasing the flow through the nonlinear networks also increases the number of cycles and leads to a narrower distribution of chemical potentials. We conclude that the relation between distribution of dissipation, network topology and strength of disequilibrium is nontrivial and can be studied systematically by artificial reaction networks. PMID:25723751

Vibrations At Surfaces During Heterogeneous Catalytic Reactions

NASA Astrophysics Data System (ADS)

Aragno, A.; Basini, Luca; Marchionna, M.; Raffaelli, A.

1989-12-01

FTIR spectroscopies can be used in a wide range of temperature and pressure conditions to investigate on the chemistry and the physics of heterogeneous catalytic reactions. In this paper we have shortly discussed the spectroscopic results obtained during the study of two different reactions; the skeletal isomerization of 1-butene to obtain 2-methylpropene and the surface aggregation and fragmentation of rhodium carbonyl complexes during thermal treatments in N2, H2, CO, CH4 atmospheres. In the first case high temperature proton tran-sfer reactions are proposed to be responsible for the skeletal isomerization reaction. In the second case our experiments have shown a partial reversibility of the nucleation processes at the surfaces and revealed a low temperature reactivity of methane on rhodium car-bonyl surface complexes.

Capture reactions on C-14 in nonstandard big bang nucleosynthesis

NASA Technical Reports Server (NTRS)

Wiescher, Michael; Gorres, Joachim; Thielemann, Friedrich-Karl

1990-01-01

Nonstandard big bang nucleosynthesis leads to the production of C-14. The further reaction path depends on the depletion of C-14 by either photon, alpha, or neutron capture reactions. The nucleus C-14 is of particular importance in these scenarios because it forms a bottleneck for the production of heavier nuclei A greater than 14. The reaction rates of all three capture reactions at big bang conditions are discussed, and it is shown that the resulting reaction path, leading to the production of heavier elements, is dominated by the (p, gamma) and (n, gamma) rates, contrary to earlier suggestions.

Iridium-Catalyzed Hydrogen Transfer Reactions

NASA Astrophysics Data System (ADS)

Saidi, Ourida; Williams, Jonathan M. J.

This chapter describes the application of iridium complexes to catalytic hydrogen transfer reactions. Transfer hydrogenation reactions provide an alternative to direct hydrogenation for the reduction of a range of substrates. A hydrogen donor, typically an alcohol or formic acid, can be used as the source of hydrogen for the reduction of carbonyl compounds, imines, and alkenes. Heteroaromatic compounds and even carbon dioxide have also been reduced by transfer hydrogenation reactions. In the reverse process, the oxidation of alcohols to carbonyl compounds can be achieved by iridium-catalyzed hydrogen transfer reactions, where a ketone or alkene is used as a suitable hydrogen acceptor. The reversible nature of many hydrogen transfer processes has been exploited for the racemization of alcohols, where temporary removal of hydrogen generates an achiral ketone intermediate. In addition, there is a growing body of work where temporary removal of hydrogen provides an opportunity for using alcohols as alkylating agents. In this chemistry, an iridium catalyst "borrows" hydrogen from an alcohol to give an aldehyde or ketone intermediate, which can be transformed into either an imine or alkene under the reaction conditions. Return of the hydrogen from the catalyst provides methodology for the formation of amines or C-C bonds where the only by-product is typically water.

Engaging unactivated alkyl, alkenyl and aryl iodides in visible-light-mediated free radical reactions

NASA Astrophysics Data System (ADS)

Nguyen, John D.; D'Amato, Erica M.; Narayanam, Jagan M. R.; Stephenson, Corey R. J.

2012-10-01

Radical reactions are a powerful class of chemical transformations. However, the formation of radical species to initiate these reactions has often required the use of stoichiometric amounts of toxic reagents, such as tributyltin hydride. Recently, the use of visible-light-mediated photoredox catalysis to generate radical species has become popular, but the scope of these radical precursors has been limited. Here, we describe the identification of reaction conditions under which photocatalysts such as fac-Ir(ppy)3 can be utilized to form radicals from unactivated alkyl, alkenyl and aryl iodides. The generated radicals undergo reduction via hydrogen atom abstraction or reductive cyclization. The reaction protocol utilizes only inexpensive reagents, occurs under mild reaction conditions, and shows exceptional functional group tolerance. Reaction efficiency is maintained upon scale-up and decreased catalyst loading, and the reaction time can be significantly shortened when the reaction is performed in a flow reactor.

Regulation of lecithin-cholesterol acyltransferase reaction by acyl acceptors and demonstration of its "idling" reaction.

PubMed

Czarnecka, H; Yokoyama, S

1993-09-15

The mechanism for regulation of cholesterol esterification by lecithin-cholesterol acyltransferase (LCAT) was studied using the highly isolated enzyme from pig plasma. In the reaction with phosphatidylcholine small unilamellar vesicles, cholesterol, water, diacylglycerol, and lysophosphatidylcholine were all potent acceptors of an acyl group cleaved from the sn-2 position of egg phosphatidylcholine, generating cholesteryl ester, free fatty acid, triglyceride, and phosphatidylcholine, respectively. All of these reactions required activation by human apolipoprotein A-I, suggesting that this activation leads to the deacylation of phosphatidylcholine. Those acceptors competed against each other in this vesicle reaction system, and cholesterol was the most potent acyl acceptor. Lysophosphatidylcholine that was endogenously generated by deacylation of phosphatidylcholine in the first step of the LCAT reaction was also a good acyl acceptor, showing that the reaction is always partly "idling." Bovine serum albumin partially inhibited this idling reaction in a concentration-dependent manner up to 80% at 0.60 mM. The above results were essentially reproducible with high density lipoprotein, except that cholesterol is less potent than lysophosphatidylcholine in accepting the acyl group under the condition used. Unlike the apolipoprotein A-I-activated reaction, cholesterol was esterified only slightly by the LCAT reaction on low density lipoprotein and, consequently, did not compete against lysophosphatidylcholine for generation of phosphatidylcholine. Thus, apoB may activate LCAT in a very different manner from apoA-I. The rate of esterification of lysophosphatidylcholine on low density lipoprotein was one-tenth of that on the vesicles and on high density lipoprotein. Thus, LCAT is active on low density lipoprotein but mostly idling as deacylating and reacylating glycerophospholipids.

Contribution to an effective design method for stationary reaction-diffusion patterns.

PubMed

Szalai, István; Horváth, Judit; De Kepper, Patrick

2015-06-01

The British mathematician Alan Turing predicted, in his seminal 1952 publication, that stationary reaction-diffusion patterns could spontaneously develop in reacting chemical or biochemical solutions. The first two clear experimental demonstrations of such a phenomenon were not made before the early 1990s when the design of new chemical oscillatory reactions and appropriate open spatial chemical reactors had been invented. Yet, the number of pattern producing reactions had not grown until 2009 when we developed an operational design method, which takes into account the feeding conditions and other specificities of real open spatial reactors. Since then, on the basis of this method, five additional reactions were shown to produce stationary reaction-diffusion patterns. To gain a clearer view on where our methodical approach on the patterning capacity of a reaction stands, numerical studies in conditions that mimic true open spatial reactors were made. In these numerical experiments, we explored the patterning capacity of Rabai's model for pH driven Landolt type reactions as a function of experimentally attainable parameters that control the main time and length scales. Because of the straightforward reversible binding of protons to carboxylate carrying polymer chains, this class of reaction is at the base of the chemistry leading to most of the stationary reaction-diffusion patterns presently observed. We compare our model predictions with experimental observations and comment on agreements and differences.

Decarboxylative aldol reactions of allyl beta-keto esters via heterobimetallic catalysis.

PubMed

Lou, Sha; Westbrook, John A; Schaus, Scott E

2004-09-22

Mild and selective heterobimetallic-catalyzed decarboxylative aldol reactions involving allyl beta-keto esters have been developed. The reaction is promoted by Pd(0)- and Yb(III)-DIOP complexes at room temperature and involves the in situ formation of a ketone enolate from allyl beta-keto esters followed by addition of the enolate to aldehydes. The reaction is a new example of heterobimetallic catalysis in which the optimized reaction conditions require the addition of both metals.

Adsorption Isotherms and Surface Reaction Kinetics

ERIC Educational Resources Information Center

Lobo, L. S.; Bernardo, C. A.

1974-01-01

Explains an error that occurs in calculating the conditions for a maximum value of a rate expression for a bimolecular reaction. The rate expression is derived using the Langmuir adsorption isotherm to relate gas pressures and corresponding surface coverages. (GS)

Three-body radiative capture reactions

NASA Astrophysics Data System (ADS)

Casal, J.; Rodríguez-Gallardo, M.; Arias, J. M.; Gómez-Camacho, J.

2018-01-01

Radiative capture reaction rates for 6He, 9Be and 17Ne formation at astrophysical conditions are studied within a three-body model using the analytical transformed harmonic oscillator method to calculate their states. An alternative procedure to estimate these rates from experimental data on low-energy breakup is also discussed.

Simultaneous determination of main reaction components in the reaction mixture during biodiesel production.

PubMed

Sánek, Lubomír; Pecha, Jiří; Kolomazník, Karel

2013-03-01

The proposed analytical method allows for simultaneous determination by GC using a programed temperature vaporization injector and a flame ionization detector of the main reaction components (i.e. glycerol, methyl esters, mono-, di-, and triacylglycerols) in the reaction mixture during biodiesel production. The suggested method is convenient for the rapid and simple evaluation of the kinetic data gained during the transesterification reaction and, also partially serves as an indicator of the quality of biodiesel and mainly, as the indicator of the efficiency of the whole production process (i.e. the conversion of triacylglycerols to biodiesel and its time progress). The optimization of chromatographic conditions (e.g. the oven temperature program, injector setting, amount of derivatization reagent, and the derivatization reaction time) was performed. The method has been validated with crude samples of biodiesel made from waste-cooking oils in terms of linearity, precision, accuracy, sensitivity, and limits of detection and quantification. The results confirmed a satisfactory degree of accuracy and repeatability (the mean RSDs were usually below 2%) necessary for the reliable quantitative determination of all components in the considerable concentration range (e.g. 10-1100 μg/mL in case of methyl esters). Compound recoveries ranging from 96 to 104% were obtained. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Copper-nicotinamide complex: sustainable applications in coupling and cycloaddition reactions

EPA Science Inventory

Crystalline copper (II)-nicotinamide complex, synthesized via simple mixing of copper chloride and nicotinamide solution at room temperature, catalyzes the C-S, C-N bond forming and cycloaddition reactions under a variety of sustainable reaction conditions.

Liquid-assisted grinding and ion pairing regulates percentage conversion and diastereoselectivity of the Wittig reaction under mechanochemical conditions.

PubMed

Denlinger, Kendra Leahy; Ortiz-Trankina, Lianna; Carr, Preston; Benson, Kingsley; Waddell, Daniel C; Mack, James

2018-01-01

Mechanochemistry is maturing as a discipline and continuing to grow, so it is important to continue understanding the rules governing the system. In a mechanochemical reaction, the reactants are added into a vessel along with one or more grinding balls and the vessel is shaken at high speeds to facilitate a chemical reaction. The dielectric constant of the solvent used in liquid-assisted grinding (LAG) and properly chosen counter-ion pairing increases the percentage conversion of stilbenes in a mechanochemical Wittig reaction. Utilizing stepwise addition/evaporation of ethanol in liquid-assisted grinding also allows for the tuning of the diastereoselectivity in the Wittig reaction.

Spent fuel reaction - the behavior of the {epsilon}-phase over 3.1 years

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

Finn, P.A.; Hoh, J.C.; Wolf, S.F.

The release fractions of the five elements in the {epsilon}-phase ({sup 99}Tc, {sup 97}Mo, Ru, Rh, and Pd) as well as that of {sup 238}U are reported for the reaction of two oxide fuels (ATM-103 and ATM-106) in unsaturated tests under oxidizing conditions. The {sup 99}Tc release fractions provide a lower limit for the magnitude of the spent fuel reaction. The {sup 99}Tc release fractions indicate that a surface reaction might be the rate controlling mechanism for fuel reaction under unsaturated conditions and the oxidant is possibly H{sub 2}O{sub 2}, a product of alpha radiolysis of water.

Solvent-free cross-dehydrogenative coupling reactions under high speed ball-milling conditions applied to the synthesis of functionalized tetrahydroisoquinolines.

PubMed

Su, Weike; Yu, Jingbo; Li, Zhenhua; Jiang, Zhijiang

2011-11-04

Solvent-free reaction using a high-speed ball milling technique has been first applied to cross-dehydrogenative coupling (CDC) reactions between tetrahydroisoquinolines and three types of pronucleophiles such as nitroalkanes, alkynes, and indoles. All coupling products were obtained in good yields at short reaction times (no more than 40 min). When alkynes and indoles were used as pronucleophile, the reactions can be catalyzed efficiently by recoverable copper balls without any additional metal catalyst.

Anodic Cyclization Reactions and the Mechanistic Strategies That Enable Optimization.

PubMed

Feng, Ruozhu; Smith, Jake A; Moeller, Kevin D

2017-09-19

Oxidation reactions are powerful tools for synthesis because they allow us to reverse the polarity of electron-rich functional groups, generate highly reactive intermediates, and increase the functionality of molecules. For this reason, oxidation reactions have been and continue to be the subject of intense study. Central to these efforts is the development of mechanism-based strategies that allow us to think about the reactive intermediates that are frequently central to the success of the reactions and the mechanistic pathways that those intermediates trigger. For example, consider oxidative cyclization reactions that are triggered by the removal of an electron from an electron-rich olefin and lead to cyclic products that are functionalized for further elaboration. For these reactions to be successful, the radical cation intermediate must first be generated using conditions that limit its polymerization and then channeled down a productive desired pathway. Following the cyclization, a second oxidation step is necessary for product formation, after which the resulting cation must be quenched in a controlled fashion to avoid undesired elimination reactions. Problems can arise at any one or all of these steps, a fact that frequently complicates reaction optimization and can discourage the development of new transformations. Fortunately, anodic electrochemistry offers an outstanding opportunity to systematically probe the mechanism of oxidative cyclization reactions. The use of electrochemical methods allows for the generation of radical cations under neutral conditions in an environment that helps prevent polymerization of the intermediate. Once the intermediates have been generated, a series of "telltale indicators" can be used to diagnose which step in an oxidative cyclization is problematic for less successful transformation. A set of potential solutions to address each type of problem encountered has been developed. For example, problems with the initial

Synthesis of Aminofuran-Linked Benzimidazoles and Cyanopyrrole-Fused Benzimidazoles by Condition-Based Skeletal Divergence.

PubMed

Hsu, Wei-Shun; Tsai, Min-Huan; Barve, Indrajeet J; Yellol, Gorakh S; Sun, Chung-Ming

2017-07-10

A condition-based skeletal divergent synthesis was explored to achieve skeletal diversity in two component condensation reaction. Cyanomethyl benzimidazole was reacted with α-bromoketone under thermal conditions to furnish 2-aminofuranyl-benzimidazoles, while the same reaction afforded 3-cyano-benzopyrrolo-imidazoles under microwave irradiation. Two nonequivalent nucleophilic centers on benzimidazole moiety were manipulated elegantly by different reaction conditions to achieve the skeletal diversity.

Reaction kinetics of cellulose hydrolysis in subcritical and supercritical water

NASA Astrophysics Data System (ADS)

Olanrewaju, Kazeem Bode

The uncertainties in the continuous supply of fossil fuels from the crisis-ridden oil-rich region of the world is fast shifting focus on the need to utilize cellulosic biomass and develop more efficient technologies for its conversion to fuels and chemicals. One such technology is the rapid degradation of cellulose in supercritical water without the need for an enzyme or inorganic catalyst such as acid. This project focused on the study of reaction kinetics of cellulose hydrolysis in subcritical and supercritical water. Cellulose reactions at hydrothermal conditions can proceed via the homogeneous route involving dissolution and hydrolysis or the heterogeneous path of surface hydrolysis. The work is divided into three main parts. First, the detailed kinetic analysis of cellulose reactions in micro- and tubular reactors was conducted. Reaction kinetics models were applied, and kinetics parameters at both subcritical and supercritical conditions were evaluated. The second major task was the evaluation of yields of water soluble hydrolysates obtained from the hydrolysis of cellulose and starch in hydrothermal reactors. Lastly, changes in molecular weight distribution due to hydrothermolytic degradation of cellulose were investigated. These changes were also simulated based on different modes of scission, and the pattern generated from simulation was compared with the distribution pattern from experiments. For a better understanding of the reaction kinetics of cellulose in subcritical and supercritical water, a series of reactions was conducted in the microreactor. Hydrolysis of cellulose was performed at subcritical temperatures ranging from 270 to 340 °C (tau = 0.40--0.88 s). For the dissolution of cellulose, the reaction was conducted at supercritical temperatures ranging from 375 to 395 °C (tau = 0.27--0.44 s). The operating pressure for the reactions at both subcritical and supercritical conditions was 5000 psig. The results show that the rate-limiting step in

Independence of reaction time and response force control during isometric leg extension.

PubMed

Fukushi, Tamami; Ohtsuki, Tatsuyuki

2004-04-01

In this study, we examined the relative control of reaction time and force in responses of the lower limb. Fourteen female participants (age 21.2 +/- 1.0 years, height 1.62 +/- 0.05 m, body mass 54.1 +/- 6.1 kg; mean +/- s) were instructed to exert their maximal isometric one-leg extension force as quickly as possible in response to an auditory stimulus presented after one of 13 foreperiod durations, ranging from 0.5 to 10.0 s. In the 'irregular condition' each foreperiod was presented in random order, while in the 'regular condition' each foreperiod was repeated consecutively. A significant interactive effect of foreperiod duration and regularity on reaction time was observed (P < 0.001 in two-way ANOVA with repeated measures). In the irregular condition the shorter foreperiod induced a longer reaction time, while in the regular condition the shorter foreperiod induced a shorter reaction time. Peak amplitude of isometric force was affected only by the regularity of foreperiod and there was a significant variation of changes in peak force across participants; nine participants were shown to significantly increase peak force for the regular condition (P < 0.001), three to decrease it (P < 0.05) and two showed no difference. These results indicate the independence of reaction time and response force control in the lower limb motor system. Variation of changes in peak force across participants may be due to the different attention to the bipolar nature of the task requirements such as maximal force and maximal speed.

Microphotochemistry: 4,4'-Dimethoxybenzophenone mediated photodecarboxylation reactions involving phthalimides

PubMed Central

Shvydkiv, Oksana; Nolan, Kieran

2011-01-01

Summary A series of 4,4'-dimethoxybenzophenone mediated intra- and intermolecular photodecarboxylation reactions involving phthalimides have been examined under microflow conditions. Conversion rates, isolated yields and chemoselectivities were compared to analogous reactions in a batch photoreactor. In all cases investigated, the microreactions gave superior results thus proving the superiority of microphotochemistry over conventional technologies. PMID:21915208

Chain-reaction crash in traffic flow controlled by taillights

NASA Astrophysics Data System (ADS)

Nagatani, Takashi

2015-02-01

We study the chain-reaction crash (multiple-vehicle collision) in low-visibility condition on a road. In the traffic situation, drivers brake according to taillights of the forward vehicle. The first crash may induce more collisions. We investigate whether or not the first collision induces the chain-reaction crash, numerically and analytically. The dynamic transitions occur from no collisions through a single collision, double collisions and triple collisions, to multiple collisions with decreasing the headway. Also, we find that the dynamic transition occurs from the finite chain reaction to the infinite chain reaction when the headway is less than the critical value. We derive, analytically, the transition points and the region maps for the chain-reaction crash in traffic flow controlled by taillights.

Cutaneous and systemic hypersensitivity reactions to metallic implants.

PubMed

Basko-Plluska, Juliana L; Thyssen, Jacob P; Schalock, Peter C

2011-01-01

Cutaneous reactions to metal implants, orthopedic or otherwise, are well documented in the literature. The first case of a dermatitis reaction over a stainless steel fracture plate was described in 1966. Most skin reactions are eczematous and allergic in nature, although urticarial, bullous, and vasculitic eruptions may occur. Also, more complex immune reactions may develop around the implants, resulting in pain, inflammation, and loosening. Nickel, cobalt, and chromium are the three most common metals that elicit both cutaneous and extracutaneous allergic reactions from chronic internal exposure. However, other metal ions as well as bone cement components can cause such hypersensitivity reactions. To complicate things, patients may also develop delayed-type hypersensitivity reactions to metals (ie, in-stent restenosis, prosthesis loosening, inflammation, pain, or allergic contact dermatitis) following the insertion of intravascular stents, dental implants, cardiac pacemakers, or implanted gynecologic devices. Despite repeated attempts by researchers and clinicians to further understand this difficult area of medicine, the association between metal sensitivity and cutaneous allergic reactions remains to be fully understood. This review provides an update of the current knowledge in this field and should be valuable to health care providers who manage patients with conditions related to this field.

Tropospheric reactions of the haloalkyl radicals formed from hydroxyl radical reaction with a series of alternative fluorocarbons

NASA Technical Reports Server (NTRS)

Atkinson, Roger

1990-01-01

In the present assessment, the hydrogen containing halocarbons being considered as alternatives to the the presently used chlorofluorocarbons are the hydrochlorofluorocarbons (HCFCs) 123 (CF3CHCl2), 141b (CFCl2CH3), 142b (CF2ClCH3), 22 (CHF2Cl) and 124 (CF3CHFCl) and the hydrofluorocarbons (HFCs) 134a (CF3CH2F), 152a (CHF2CH3) and 125 (CF3CHF2). All of these HCFCs and HFCs will react with the hydroxyl (OH) radical in the troposphere, giving rise to haloalkyl radicals which then undergo a complex series of reactions in the troposphere. These reactions of the haloalkyl radicals formed from the initial OH radical reactions with the HCFCs and HFCs under tropospheric conditions are the focus here.

New Complexity-Building Reactions of Alpha-Keto Esters

NASA Astrophysics Data System (ADS)

Bartlett, Samuel L.

I. Introduction: Importance of Asymmetric Catalysis and the Reactivity Patterns of alpha-Keto Esters. II. Synthesis of Complex Tertiary Glycolates by Enantioconvergent Arylation of Stereochemically Labile alpha-Keto Esters. Enantioconvergent arylation reactions of boronic acids and racemic ?-stereogenic alpha-keto esters have been developed. The reactions are catalyzed by a chiral (diene)Rh(I) complex and provide a wide array of beta-stereogenic tertiary aryl glycolate derivatives with high levels of diastereo- and enantioselectivity. Racemization studies employing a series of sterically differentiated tertiary amines suggest that the steric nature of the amine base additive exerts a significant influence on the rate of substrate racemization. III. Palladium-Catalyzed beta-Arylation of alpha-Keto Esters . A catalyst system derived from commercially available Pd2(dba) 3 and PtBu3 has been applied to the coupling of alpha-keto ester enolates and aryl bromides. The reaction provides access to an array of beta-stereogenic alpha-keto ester derivatives. When the air stable ligand precursor PtBu 3˙HBF4 is employed, the reaction can be carried out without use of a glovebox. The derived products are of broad interest given the prevalence of the alpha-keto acid substructure in biologically important molecules. IV. Catalytic Enantioselective [3+2] Cycloaddition of alpha-Keto Ester Enolates and Nitrile Oxides. An enantioselective [3+2] cycloaddition reaction between nitrile oxides and transiently generated enolates of alpha-keto esters has been developed. The catalyst system was found to be compatible with in situ nitrile oxide generation conditions. A versatile array of nitrile oxides and alpha-keto esters could participate in the cycloaddition, providing novel 5-hydroxy-2-isoxazolines in high chemical yield with high levels of diastereo- and enantioselectivity. Notably, the optimal reaction conditions circumvented concurrent reaction via O-imidoylation and hetero-[3

A computational approach to extinction events in chemical reaction networks with discrete state spaces.

PubMed

Johnston, Matthew D

2017-12-01

Recent work of Johnston et al. has produced sufficient conditions on the structure of a chemical reaction network which guarantee that the corresponding discrete state space system exhibits an extinction event. The conditions consist of a series of systems of equalities and inequalities on the edges of a modified reaction network called a domination-expanded reaction network. In this paper, we present a computational implementation of these conditions written in Python and apply the program on examples drawn from the biochemical literature. We also run the program on 458 models from the European Bioinformatics Institute's BioModels Database and report our results. Copyright © 2017 Elsevier Inc. All rights reserved.

Loss of Functional Photosystem II Reaction Centres in Zooxanthellae of Corals Exposed to Bleaching Conditions: Using Fluorescence Rise Kinetics.

PubMed

Hill, R; Larkum, A W D; Frankart, C; Kühl, M; Ralph, P J

2004-01-01

Mass coral bleaching is linked to elevated sea surface temperatures, 1-2 degrees C above average, during periods of intense light. These conditions induce the expulsion of zooxanthellae from the coral host in response to photosynthetic damage in the algal symbionts. The mechanism that triggers this release has not been clearly established and to further our knowledge of this process, fluorescence rise kinetics have been studied for the first time. Corals that were exposed to elevated temperature (33 degrees C) and light (280 mumol photons m(-2) s(-1)), showed distinct changes in the fast polyphasic induction of chlorophyll-a fluorescence, indicating biophysical changes in the photochemical processes. The fluorescence rise over the first 2000ms was monitored in three species of corals for up to 8 h, with a PEA fluorometer and an imaging-PAM. Pocillopora damicornis showed the least impact on photosynthetic apparatus, while Acropora nobilis was the most sensitive, with Cyphastrea serailia intermediate between the other two species. A. nobilis showed a remarkable capacity for recovery from bleaching conditions. For all three species, a steady decline in the slope of the initial rise and the height of the J-transient was observed, indicating the loss of functional Photosystem II (PS II) centres under elevated-temperature conditions. A significant loss of PS II centres was confirmed by a decline in photochemical quenching when exposed to bleaching stress. Non-photochemical quenching was identified as a significant mechanism for dissipating excess energy as heat under the bleaching conditions. Photophosphorylation could explain this decline in PS II activity. State transitions, a component of non-photochemical quenching, was a probable cause of the high non-photochemical quenching during bleaching and this mechanism is associated with the phosphorylation-induced dissociation of the light harvesting complexes from the PS II reaction centres. This reversible process may

Lagrangian descriptors of driven chemical reaction manifolds.

PubMed

Craven, Galen T; Junginger, Andrej; Hernandez, Rigoberto

2017-08-01

The persistence of a transition state structure in systems driven by time-dependent environments allows the application of modern reaction rate theories to solution-phase and nonequilibrium chemical reactions. However, identifying this structure is problematic in driven systems and has been limited by theories built on series expansion about a saddle point. Recently, it has been shown that to obtain formally exact rates for reactions in thermal environments, a transition state trajectory must be constructed. Here, using optimized Lagrangian descriptors [G. T. Craven and R. Hernandez, Phys. Rev. Lett. 115, 148301 (2015)PRLTAO0031-900710.1103/PhysRevLett.115.148301], we obtain this so-called distinguished trajectory and the associated moving reaction manifolds on model energy surfaces subject to various driving and dissipative conditions. In particular, we demonstrate that this is exact for harmonic barriers in one dimension and this verification gives impetus to the application of Lagrangian descriptor-based methods in diverse classes of chemical reactions. The development of these objects is paramount in the theory of reaction dynamics as the transition state structure and its underlying network of manifolds directly dictate reactivity and selectivity.

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.

Prompt HO2 formation following the reaction of OH with aromatic compounds under atmospheric conditions.

PubMed

Nehr, Sascha; Bohn, Birger; Wahner, Andreas

2012-06-21

The secondary formation of HO(2) radicals following OH + aromatic hydrocarbon reactions in synthetic air under normal pressure and temperature was investigated in the absence of NO after pulsed production of OH radicals. OH and HO(x) (=OH + HO(2)) decay curves were recorded using laser-induced fluorescence after gas-expansion. The prompt HO(2) yields (HO(2) formed without preceding NO reactions) were determined by comparison to results obtained with CO as a reference compound. This approach was recently introduced and applied to the OH + benzene reaction and was extended here for a number of monocyclic aromatic hydrocarbons. The measured HO(2) formation yields are as follows: toluene, 0.42 ± 0.11; ethylbenzene, 0.53 ± 0.10; o-xylene, 0.41 ± 0.08; m-xylene, 0.27 ± 0.06; p-xylene, 0.40 ± 0.09; 1,2,3-trimethylbenzene, 0.31 ± 0.06; 1,2,4-trimethylbenzene, 0.37 ± 0.09; 1,3,5-trimethylbenzene, 0.29 ± 0.08; hexamethylbenzene, 0.32 ± 0.08; phenol, 0.89 ± 0.29; o-cresol, 0.87 ± 0.29; 2,5-dimethylphenol, 0.72 ± 0.12; 2,4,6-trimethylphenol, 0.45 ± 0.13. For the alkylbenzenes HO(2) is the proposed coproduct of phenols, epoxides, and possibly oxepins formed in secondary reactions with O(2). In most product studies the only quantified coproducts were phenols whereas only a few studies reported yields of epoxides. Oxepins have not been observed so far. Together with the yields of phenols from other studies, the HO(2) yields determined in this work set an upper limit to the combined yields of epoxides and oxepins that was found to be significant (≤0.3) for all investigated alkylbenzenes except m-xylene. For the hydroxybenzenes the currently proposed HO(2) coproducts are dihydroxybenzenes. For phenol and o-cresol the determined HO(2) yields are matching the previously reported dihydroxybenzene yields, indicating that these are the only HO(2) forming reaction channels. For 2,5-dimethylphenol and 2,4,6-trimethylphenol no complementary product studies are available.

Double stratified radiative Jeffery magneto nanofluid flow along an inclined stretched cylinder with chemical reaction and slip condition

NASA Astrophysics Data System (ADS)

Ramzan, M.; Gul, Hina; Dong Chung, Jae

2017-11-01

A mathematical model is designed to deliberate the flow of an MHD Jeffery nanofluid past a vertically inclined stretched cylinder near a stagnation point. The flow analysis is performed in attendance of thermal radiation, mixed convection and chemical reaction. Influence of thermal and solutal stratification with slip boundary condition is also considered. Apposite transformations are engaged to convert the nonlinear partial differential equations to differential equations with high nonlinearity. Convergent series solutions of the problem are established via the renowned Homotopy Analysis Method (HAM). Graphical illustrations are plotted to depict the effects of prominent arising parameters against all involved distributions. Numerically erected tables of important physical parameters like Skin friction, Nusselt and Sherwood numbers are also give. Comparative studies (with a previously examined work) are also included to endorse our results. It is noticed that the thermal stratification parameter has diminishing effect on temperature distribution. Moreover, the velocity field is a snowballing and declining function of curvature and slip parameters respectively.

Detailed surface reaction mechanism in a three-way catalyst.

PubMed

Chatterjee, D; Deutschmann, O; Warnatz, J

2001-01-01

Monolithic three-way catalysts are applied to reduce the emission of combustion engines. The design of such a catalytic converter is a complex process involving the optimization of different physical and chemical parameters (in the simplest case, e.g., length, cell densities or metal coverage of the catalyst). Numerical simulation can be used as an effective tool for the investigation of the catalytic properties of a catalytic converter and for the prediction of the performance of the catalyst. To attain this goal, a two-dimensional flow-field description is coupled with a detailed surface reaction model (gas-phase reactions can be neglected in three-way catalysts). This surface reaction mechanism (with C3H6 taken as representative of unburnt hydrocarbons) was developed using sub-mechanisms recently developed for hydrogen, carbon monoxide and methane oxidation, literature values for C3H6 oxidation, and estimates for the remaining unknown reactions. Results of the simulation of a monolithic single channel are used to validate the surface reaction mechanism. The performance of the catalyst was simulated under lean, nearly stoichiometric and rich conditions. For these characteristic conditions, the oxidation of propene and carbon monoxide and the reduction of NO on a typical Pt/Rh coated three-way catalyst were simulated as a function of temperature. The numerically predicted conversion data are compared with experimentally measured data. The simulation further reveals the coupling between chemical reactions and transport processes within the monolithic channel.

Covalent binding of aniline to humic substances. 2. 15N NMR studies of nucleophilic addition reactions

USGS Publications Warehouse

Thorn, K.A.; Pettigrew, P.J.; Goldenberg, W.S.; Weber, E.J.

1996-01-01

Aromatic amines are known to undergo covalent binding with humic substances in the environment. Although previous studies have examined reaction conditions and proposed mechanisms, there has been no direct spectroscopic evidence for the covalent binding of the amines to the functional groups in humic substances. In order to further elucidate the reaction mechanisms, the Suwannee River and IHSS soil fulvic and humic acids were reacted with 15N-labeled aniline at pH 6 and analyzed using 15N NMR spectrometry. Aniline underwent nucleophilic addition reactions with the quinone and other carbonyl groups in the samples and became incorporated in the form of anilinohydroquinone, anilinoquinone, anilide, imine, and heterocyclic nitrogen, the latter comprising 50% or more of the bound amine. The anilide and anilinohydroquinone nitrogens were determined to be susceptible to chemical exchange by ammonia. In the case of Suwannee River fulvic acid, reaction under anoxic conditions and pretreatment with sodium borohydride or hydroxylamine prior to reaction under oxic conditions resulted in a decrease in the proportion of anilinohydroquinone nitrogen incorporated. The relative decrease in the incorporation of anilinohydroquinone nitrogen with respect to anilinoquinone nitrogen under anoxic conditions suggested that inter- or intramolecular redox reactions accompanied the nucleophilic addition reactions.

Trimolecular reactions of uranium hexafluoride with water.

PubMed

Lind, Maria C; Garrison, Stephen L; Becnel, James M

2010-04-08

The hydrolysis reaction of uranium hexafluoride (UF(6)) is a key step in the synthesis of uranium dioxide (UO(2)) powder for nuclear fuels. Mechanisms for the hydrolysis reactions are studied here with density functional theory and the Stuttgart small-core scalar relativistic pseudopotential and associated basis set for uranium. The reaction of a single UF(6) molecule with a water molecule in the gas phase has been previously predicted to proceed over a relatively sizable barrier of 78.2 kJ x mol(-1), indicating this reaction is only feasible at elevated temperatures. Given the observed formation of a second morphology for the UO(2) product coupled with the observations of rapid, spontaneous hydrolysis at ambient conditions, an alternate reaction pathway must exist. In the present work, two trimolecular hydrolysis mechanisms are studied with density functional theory: (1) the reaction between two UF(6) molecules and one water molecule, and (2) the reaction of two water molecules with a single UF(6) molecule. The predicted reaction of two UF(6) molecules with one water molecule displays an interesting "fluorine-shuttle" mechanism, a significant energy barrier of 69.0 kJ x mol(-1) to the formation of UF(5)OH, and an enthalpy of reaction (DeltaH(298)) of +17.9 kJ x mol(-1). The reaction of a single UF(6) molecule with two water molecules displays a "proton-shuttle" mechanism, and is more favorable, having a slightly lower computed energy barrier of 58.9 kJ x mol(-1) and an exothermic enthalpy of reaction (DeltaH(298)) of -13.9 kJ x mol(-1). The exothermic nature of the overall UF(6) + 2H(2)O trimolecular reaction and the lowering of the barrier height with respect to the bimolecular reaction are encouraging.

Copper(II) carboxylate promoted intramolecular diamination of terminal alkenes: improved reaction conditions and expanded substrate scope.

PubMed

Zabawa, Thomas P; Chemler, Sherry R

2007-05-10

The copper(II) carboxylate promoted diamination reaction has been improved by the use of the organic soluble copper(II) neodecanoate [Cu(ND)2]. Cu(ND)2 allowed the less-polar solvent dichloroethane (DCE) to be used, and as a consequence, decomposition of less-reactive substrates could be avoided. High diastereoselectivity was observed in the synthesis of 2,5-disubstituted pyrrolidines. Ureas, bis(anilines), and alpha-amido pyrroles derived from 2-allylaniline could also participate in the diamination reaction.

Mechanism and scope of the cyanide-catalyzed cross silyl benzoin reaction.

PubMed

Linghu, Xin; Bausch, Cory C; Johnson, Jeffrey S

2005-02-16

In this work, cross silyl benzoin addition reactions between acylsilanes (1) and aldehydes (2) catalyzed by metal cyanides are described. Unsymmetrical aryl-, heteroaryl-, and alkyl-substituted benzoin adducts can be generated in moderate to excellent yields with complete regiocontrol using potassium cyanide and a phase transfer catalyst. From a screen of transition metal cyanide complexes, lanthanum tricyanide was identified as an improved second-generation catalyst for the cross silyl benzoin reaction. A study of the influence of water on the KCN-catalyzed cross silyl benzoin addition revealed more practical reaction conditions using unpurified solvent under ambient conditions. A sequential silyl benzoin addition/cyanation/O-acylation reaction that resulted in two new C-C bonds was achieved in excellent yield. The mechanism of cross silyl benzoin addition is proposed in detail and is supported by crossover studies and a number of unambiguous experiments designed to ascertain the reversibility of key steps. No productive chemistry arises from cyanation of the more electrophilic aldehyde component. Formation of the carbon-carbon bond is shown to be the last irreversible step in the reaction.

Conditions for diffusion-limited and reaction-limited recombination in nanostructured solar cells

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

Ansari-Rad, Mehdi, E-mail: ansari.rad@ut.ac.ir; Department of Physics, University of Shahrood, Shahrood; Anta, Juan A., E-mail: anta@upo.es

2014-04-07

The performance of Dye-sensitized solar cells (DSC) and related devices made of nanostructured semiconductors relies on a good charge separation, which in turn is achieved by favoring charge transport against recombination. Although both processes occur at very different time scales, hence ensuring good charge separation, in certain cases the kinetics of transport and recombination can be connected, either in a direct or an indirect way. In this work, the connection between electron transport and recombination in nanostructured solar cells is studied both theoretically and by Monte Carlo simulation. Calculations using the Multiple-Trapping model and a realistic trap distribution for nanostructuredmore » TiO{sub 2} show that for attempt-to-jump frequencies higher than 10{sup 11}–10{sup 13} Hz, the system adopts a reaction limited (RL) regime, with a lifetime which is effectively independent from the speed of the electrons in the transport level. For frequencies lower than those, and depending on the concentration of recombination centers in the material, the system enters a diffusion-limited regime (DL), where the lifetime increases if the speed of free electrons decreases. In general, the conditions for RL or DL recombination depend critically on the time scale difference between recombination kinetics and free-electron transport. Hence, if the former is too rapid with respect to the latter, the system is in the DL regime and total thermalization of carriers is not possible. In the opposite situation, a RL regime arises. Numerical data available in the literature, and the behavior of the lifetime with respect to (1) density of recombination centers and (2) probability of recombination at a given center, suggest that a typical DSC in operation stays in the RL regime with complete thermalization, although a transition to the DL regime may occur for electrolytes or hole conductors where recombination is especially rapid or where there is a larger dispersion of

Reactions of ferric hemoglobin and myoglobin with hydrogen sulfide under physiological conditions.

PubMed

Jensen, Birgitte; Fago, Angela

2018-05-01

Ferric hemoglobin (metHb) and myoglobin (metMb), present at low levels in vivo, have been recently found to oxidize hydrogen sulfide (H 2 S) in excess, thus potentially contributing to removal of toxic H 2 S in blood and heart, respectively. Here, we present a kinetic and thermodynamic study of the reaction of metHb and metMb with H 2 S under physiological conditions, i.e. at low H 2 S concentrations and with protein in excess of H 2 S. We show here that both proteins react with sub-stoichiometric H 2 S:heme ratios following two processes: a fast reversible binding of H 2 S to ferric heme that prevails at high H 2 S and a slow heme reduction to the ferrous state that prevails at low H 2 S. While these two processes are fast for metMb, H 2 S-induced heme reduction is slow for metHb and the metHb-H 2 S complex once formed is therefore relatively stable. We find that metHb binds H 2 S reversibly and cooperatively with a pH-dependent ligand affinity that is within the physiological range of H 2 S concentrations found in blood. Stopped-flow kinetics show identical association rate constants for H 2 S at varying pH, demonstrating that H 2 S and not HS - enters the ferric heme pocket. Dissociation rates of the metHb-H 2 S complex increase when decreasing pH, consistent with the pH-dependent affinity. Taken together, these data are consistent with a novel biological role of metHb as a H 2 S carrier in the blood, in parallel with the oxygen carrier function of the much more abundant ferrous Hb. In contrast, metMb in the heart could participate to redox-signaling involving H 2 S. Copyright © 2018 Elsevier Inc. All rights reserved.

In situ formation of the amino sugars 1-amino-1-deoxy-fructose and 2-amino-2-deoxy-glucose under Maillard reaction conditions in the absence of ammonia.

PubMed

Nashalian, Ossanna; Yaylayan, Varoujan A

2016-04-15

Replacing amino acids with their binary metal complexes during the Maillard reaction can initiate various processes, including the oxidative degradation of their glucose conjugates, generating 1-amino-1-deoxy-fructose and its derivatives. These reactive amino sugars are not easily accessible under Maillard reaction conditions and are only formed in the presence of ammonia. To explore the generality of this observation and to study in particular the ability of fructose to generate glucosamine, the amino acid-metal complexes were heated in aqueous solutions with three aldohexoses and two ketohexoses at 110°C for 2 h and the dry residues were analysed by ESI/qTOF/MS/MS. All the sugars generated relatively intense ions at [M+H](+) 180 (C6H14NO5); those ions originating from ketohexoses exhibited MS/MS fragmentations identical to glucosamine and those originating form aldohexoses showed ions identical to fructosamine. Furthermore, the amino sugars were found to form fructosazine, react with other sugars and undergo dehydration reactions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Iterated reaction graphs: simulating complex Maillard reaction pathways.

PubMed

Patel, S; Rabone, J; Russell, S; Tissen, J; Klaffke, W

2001-01-01

This study investigates a new method of simulating a complex chemical system including feedback loops and parallel reactions. The practical purpose of this approach is to model the actual reactions that take place in the Maillard process, a set of food browning reactions, in sufficient detail to be able to predict the volatile composition of the Maillard products. The developed framework, called iterated reaction graphs, consists of two main elements: a soup of molecules and a reaction base of Maillard reactions. An iterative process loops through the reaction base, taking reactants from and feeding products back to the soup. This produces a reaction graph, with molecules as nodes and reactions as arcs. The iterated reaction graph is updated and validated by comparing output with the main products found by classical gas-chromatographic/mass spectrometric analysis. To ensure a realistic output and convergence to desired volatiles only, the approach contains a number of novel elements: rate kinetics are treated as reaction probabilities; only a subset of the true chemistry is modeled; and the reactions are blocked into groups.

Copper(II) Carboxylate Promoted Intramolecular Diamination of Terminal Alkenes: Improved Reaction Conditions and Expanded Substrate Scope

PubMed Central

Zabawa, Thomas P.

2008-01-01

The copper(II) carboxylate promoted diamination reaction has been improved by the use of the organic soluble copper(II) neodecanoate [Cu(ND)2]. Cu(ND)2 allowed the less polar solvent, dichloroethane (DCE) to be used, and as a consequence, decomposition of less reactive substrates could be avoided. High diastereoselectivity was observed in the synthesis of 2,5-disubstituted pyrrolidines. Ureas, bis(anilines) and α-amido pyrroles derived from 2-allylaniline could also participate in the diamination reaction. PMID:17447781

Catalytic reaction processes revealed by scanning probe microscopy. [corrected].

PubMed

Jiang, Peng; Bao, Xinhe; Salmeron, Miquel

2015-05-19

Heterogeneous catalysis is of great importance for modern society. About 80% of the chemicals are produced by catalytic reactions. Green energy production and utilization as well as environmental protection also need efficient catalysts. Understanding the reaction mechanisms is crucial to improve the existing catalysts and develop new ones with better activity, selectivity, and stability. Three components are involved in one catalytic reaction: reactant, product, and catalyst. The catalytic reaction process consists of a series of elementary steps: adsorption, diffusion, reaction, and desorption. During reaction, the catalyst surface can change at the atomic level, with roughening, sintering, and segregation processes occurring dynamically in response to the reaction conditions. Therefore, it is imperative to obtain atomic-scale information for understanding catalytic reactions. Scanning probe microscopy (SPM) is a very appropriate tool for catalytic research at the atomic scale because of its unique atomic-resolution capability. A distinguishing feature of SPM, compared to other surface characterization techniques, such as X-ray photoelectron spectroscopy, is that there is no intrinsic limitation for SPM to work under realistic reaction conditions (usually high temperature and high pressure). Therefore, since it was introduced in 1981, scanning tunneling microscopy (STM) has been widely used to investigate the adsorption, diffusion, reaction, and desorption processes on solid catalyst surfaces at the atomic level. STM can also monitor dynamic changes of catalyst surfaces during reactions. These invaluable microscopic insights have not only deepened the understanding of catalytic processes, but also provided important guidance for the development of new catalysts. This Account will focus on elementary reaction processes revealed by SPM. First, we will demonstrate the power of SPM to investigate the adsorption and diffusion process of reactants on catalyst surfaces

Modeling Time-Dependent Behavior of Concrete Affected by Alkali Silica Reaction in Variable Environmental Conditions.

PubMed

Alnaggar, Mohammed; Di Luzio, Giovanni; Cusatis, Gianluca

2017-04-28

Alkali Silica Reaction (ASR) is known to be a serious problem for concrete worldwide, especially in high humidity and high temperature regions. ASR is a slow process that develops over years to decades and it is influenced by changes in environmental and loading conditions of the structure. The problem becomes even more complicated if one recognizes that other phenomena like creep and shrinkage are coupled with ASR. This results in synergistic mechanisms that can not be easily understood without a comprehensive computational model. In this paper, coupling between creep, shrinkage and ASR is modeled within the Lattice Discrete Particle Model (LDPM) framework. In order to achieve this, a multi-physics formulation is used to compute the evolution of temperature, humidity, cement hydration, and ASR in both space and time, which is then used within physics-based formulations of cracking, creep and shrinkage. The overall model is calibrated and validated on the basis of experimental data available in the literature. Results show that even during free expansions (zero macroscopic stress), a significant degree of coupling exists because ASR induced expansions are relaxed by meso-scale creep driven by self-equilibriated stresses at the meso-scale. This explains and highlights the importance of considering ASR and other time dependent aging and deterioration phenomena at an appropriate length scale in coupled modeling approaches.

Modeling Time-Dependent Behavior of Concrete Affected by Alkali Silica Reaction in Variable Environmental Conditions

PubMed Central

Alnaggar, Mohammed; Di Luzio, Giovanni; Cusatis, Gianluca

2017-01-01

Alkali Silica Reaction (ASR) is known to be a serious problem for concrete worldwide, especially in high humidity and high temperature regions. ASR is a slow process that develops over years to decades and it is influenced by changes in environmental and loading conditions of the structure. The problem becomes even more complicated if one recognizes that other phenomena like creep and shrinkage are coupled with ASR. This results in synergistic mechanisms that can not be easily understood without a comprehensive computational model. In this paper, coupling between creep, shrinkage and ASR is modeled within the Lattice Discrete Particle Model (LDPM) framework. In order to achieve this, a multi-physics formulation is used to compute the evolution of temperature, humidity, cement hydration, and ASR in both space and time, which is then used within physics-based formulations of cracking, creep and shrinkage. The overall model is calibrated and validated on the basis of experimental data available in the literature. Results show that even during free expansions (zero macroscopic stress), a significant degree of coupling exists because ASR induced expansions are relaxed by meso-scale creep driven by self-equilibriated stresses at the meso-scale. This explains and highlights the importance of considering ASR and other time dependent aging and deterioration phenomena at an appropriate length scale in coupled modeling approaches. PMID:28772829

A taxonomy of integral reaction path analysis

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

Grcar, Joseph F.; Day, Marcus S.; Bell, John B.

2004-12-23

W. C. Gardiner observed that achieving understanding through combustion modeling is limited by the ability to recognize the implications of what has been computed and to draw conclusions about the elementary steps underlying the reaction mechanism. This difficulty can be overcome in part by making better use of reaction path analysis in the context of multidimensional flame simulations. Following a survey of current practice, an integral reaction flux is formulated in terms of conserved scalars that can be calculated in a fully automated way. Conditional analyses are then introduced, and a taxonomy for bidirectional path analysis is explored. Many examplesmore » illustrate the resulting path analysis and uncover some new results about nonpremixed methane-air laminar jets.« less

Effect of perception irregularity on chain-reaction crash in low visibility

NASA Astrophysics Data System (ADS)

Nagatani, Takashi

2015-06-01

We present the dynamic model of the chain-reaction crash to take into account the irregularity of the perception-reaction time. When a driver brakes according to taillights of the forward vehicle, the perception-reaction time varies from driver to driver. We study the effect of the perception irregularity on the chain-reaction crash (multiple-vehicle collision) in low-visibility condition. The first crash may induce more collisions. We investigate how the first collision induces the chain-reaction crash numerically. We derive, analytically, the transition points and the region maps for the chain-reaction crash in traffic flow of vehicles with irregular perception times. We clarify the effect of the perception irregularity on the multiple-vehicle collision.

On the Maillard reaction of meteoritic amino acids

NASA Astrophysics Data System (ADS)

Kolb, Vera M.; Bajagic, Milica; Liesch, Patrick J.; Philip, Ajish; Cody, George D.

2006-08-01

We have performed the Maillard reaction of a series of meteoritic amino acids with sugar ribose under simulated prebiotic conditions, in the solid state at 65°C and at the room temperature. Many meteoritic amino acids are highly reactive with ribose, even at the room temperature. We have isolated high molecular weight products that are insoluble in water, and have studied their structure by the IR (infrared) and solid-state C-13 NMR (nuclear magnetic resonance) spectroscopic methods. The functional groups and their distribution were similar among these products, and were comparable to the previously isolated insoluble organic materials from the Maillard reaction of the common amino acids with ribose. In addition, there were some similarities with the insoluble organic material that is found on Murchison. Our results suggest that the Maillard products may contribute to the composition of the part of the insoluble organic material that is found on Murchison. We have also studied the reaction of sodium silicate solution with the Maillard mixtures, to elucidate the process by which the organic compounds are preserved under prebiotic conditions.

Ru-Catalyzed Estragole Isomerization under Homogeneous and Ionic Liquid Biphasic Conditions

PubMed Central

2017-01-01

The isomerization of estragole to trans-anethole is an important reaction and is industrially performed using an excess of NaOH or KOH in ethanol at high temperatures with very low selectivity. Simple Ru-based transition-metal complexes, under homogeneous, ionic liquid (IL)-supported (biphasic) and “solventless” conditions, can be used for this reaction. The selectivity of this reaction is more sensitive to the solvent/support used than the ligands associated with the metal catalyst. Thus, under the optimized reaction conditions, 100% conversion can be achieved in the estragole isomerization, using as little as 4 × 10–3 mol % (40 ppm) of [RuHCl(CO)(PPh3)3] in toluene, reflecting a total turnover number (TON) of 25 000 and turnover frequencies (TOFs) of up to 500 min–1 at 80 °C. Using a dimeric Ru precursor, [RuCl(μ-Cl)(η3:η3-C10H16)]2, in ethanol associated with P(OEt)3, a TON of 10 000 and a TOF of 125 min–1 are obtained with 100% conversion and 99% selectivity. These two Ru catalytic systems can be transposed to biphasic IL systems by using ionic-tagged P-ligands such as 1-(3-(diphenylphosphanyl)propyl)-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide immobilized in 1-(3-hydroxypropyl)-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl) imide with up to 99% selectivity and almost complete estragole conversion. However, the reaction is much slower than that performed under solventless or homogeneous conditions. The use of ionic-tagged ligands significantly reduces the Ru leaching to the organic phase, compared to that in reactions performed under homogeneous conditions, where the catalytic system loses catalytic performance after the second recycling. Detailed kinetic investigations of the reaction catalyzed by [RuHCl(CO)(PPh3)3] indicate that a simplified kinetic model (a monomolecular reversible first-order reaction) is adequate for fitting the homogeneous reaction at 80 °C and under biphasic conditions. However, the kinetics of

A novel in chemico method to detect skin sensitizers in highly diluted reaction conditions.

PubMed

Yamamoto, Yusuke; Tahara, Haruna; Usami, Ryota; Kasahara, Toshihiko; Jimbo, Yoshihiro; Hioki, Takanori; Fujita, Masaharu

2015-11-01

The direct peptide reactivity assay (DPRA) is a simple and versatile alternative method for the evaluation of skin sensitization that involves the reaction of test chemicals with two peptides. However, this method requires concentrated solutions of test chemicals, and hydrophobic substances may not dissolve at the concentrations required. Furthermore, hydrophobic test chemicals may precipitate when added to the reaction solution. We previously established a high-sensitivity method, the amino acid derivative reactivity assay (ADRA). This method uses novel cysteine (NAC) and novel lysine derivatives (NAL), which were synthesized by introducing a naphthalene ring to the amine group of cysteine and lysine residues. In this study, we modified the ADRA method by reducing the concentration of the test chemicals 100-fold. We investigated the accuracy of skin sensitization predictions made using the modified method, which was designated the ADRA-dilutional method (ADRA-DM). The predictive accuracy of the ADRA-DM for skin sensitization was 90% for 82 test chemicals which were also evaluated via the ADRA, and the predictive accuracy in the ADRA-DM was higher than that in the ADRA and DPRA. Furthermore, no precipitation of test compounds was observed at the initiation of the ADRA-DM reaction. These results show that the ADRA-DM allowed the use of test chemicals at concentrations two orders of magnitude lower than that possible with the ADRA. In addition, ADRA-DM does not have the restrictions on test compound solubility that were a major problem with the DPRA. Therefore, the ADRA-DM is a versatile and useful method. Copyright © 2015 John Wiley & Sons, Ltd.

Mild and efficient molybdenum-mediated Pauson-Khand-type reaction.

PubMed

Adrio, Javier; Rivero, Marta Rodríguez; Carretero, Juan Carlos

2005-02-03

[reaction: see text] The molybdenum-mediated Pauson-Khand reaction promoted by Mo(CO)3(DMF)3 takes place under very mild conditions in the absence of any promoter. High yields in Pauson-Khand adducts are obtained in the cyclization of a wide variety of functionalized 1,6- and 1,7-enynes. Enynes bearing electron withdrawing groups at the alkene terminus are particularly good substrates.

Chronic neutrophilic leukaemia and plasma cell-related neutrophilic leukaemoid reactions.

PubMed

Bain, Barbara J; Ahmad, Shahzaib

2015-11-01

Many cases reported as 'chronic neutrophilic leukaemia' have had an associated plasma cell neoplasm. Recent evidence suggests that the great majority of such cases represent a neutrophilic leukaemoid reaction to the underlying multiple myeloma or monoclonal gammopathy of undetermined significance. We have analysed all accessible reported cases to clarify the likely diagnosis and to ascertain whether toxic granulation, Döhle bodies and an increased neutrophil alkaline phosphatase score were useful in making a distinction between chronic neutrophilic leukaemia and a neutrophilic leukaemoid reaction. We established that all these changes occur in both conditions. Toxic granulation and Döhle bodies are more consistently present in leukaemoid reactions but also occur quite frequently in chronic neutrophilic leukaemia. The neutrophil alkaline phosphatase score is increased in both conditions and is of no value in making a distinction. © 2015 John Wiley & Sons Ltd.

Signatures of a quantum diffusion limited hydrogen atom tunneling reaction.

PubMed

Balabanoff, Morgan E; Ruzi, Mahmut; Anderson, David T

2017-12-20

We are studying the details of hydrogen atom (H atom) quantum diffusion in highly enriched parahydrogen (pH 2 ) quantum solids doped with chemical species in an effort to better understand H atom transport and reactivity under these conditions. In this work we present kinetic studies of the 193 nm photo-induced chemistry of methanol (CH 3 OH) isolated in solid pH 2 . Short-term irradiation of CH 3 OH at 1.8 K readily produces CH 2 O and CO which we detect using FTIR spectroscopy. The in situ photochemistry also produces CH 3 O and H atoms which we can infer from the post-photolysis reaction kinetics that display significant CH 2 OH growth. The CH 2 OH growth kinetics indicate at least three separate tunneling reactions contribute; (i) reactions of photoproduced CH 3 O with the pH 2 host, (ii) H atom reactions with the CH 2 O photofragment, and (iii) long-range migration of H atoms and reaction with CH 3 OH. We assign the rapid CH 2 OH growth to the following CH 3 O + H 2 → CH 3 OH + H → CH 2 OH + H 2 two-step sequential tunneling mechanism by conducting analogous kinetic measurements using deuterated methanol (CD 3 OD). By performing photolysis experiments at 1.8 and 4.3 K, we show the post-photolysis reaction kinetics change qualitatively over this small temperature range. We use this qualitative change in the reaction kinetics with temperature to identify reactions that are quantum diffusion limited. While these results are specific to the conditions that exist in pH 2 quantum solids, they have direct implications on the analogous low temperature H atom tunneling reactions that occur on metal surfaces and on interstellar grains.

Autohydrolysis of agricultural residues: study of reaction byproducts.

PubMed

Garrote, Gil; Falqué, Elena; Domínguez, Herminia; Parajó, Juan Carlos

2007-07-01

Samples of rice husks and corn cobs were subjected to hydrothermal treatments in aqueous media under conditions leading to maximal xylooligomer concentration, and the reaction liquors were extracted with dichloromethane (DCM) to assess the type and amount of reaction byproducts with potential application as food ingredients and cosmetics. The identified DCM-soluble compounds were classified in four categories (sugar-derived compounds, lignin-derived compounds, nitrogen-containing compounds and fatty acids). The experimental results were compared with literature data.

General chemical kinetics computer program for static and flow reactions, with application to combustion and shock-tube kinetics

NASA Technical Reports Server (NTRS)

Bittker, D. A.; Scullin, V. J.

1972-01-01

A general chemical kinetics program is described for complex, homogeneous ideal-gas reactions in any chemical system. Its main features are flexibility and convenience in treating many different reaction conditions. The program solves numerically the differential equations describing complex reaction in either a static system or one-dimensional inviscid flow. Applications include ignition and combustion, shock wave reactions, and general reactions in a flowing or static system. An implicit numerical solution method is used which works efficiently for the extreme conditions of a very slow or a very fast reaction. The theory is described, and the computer program and users' manual are included.

Mesoscale simulations of shockwave energy dissipation via chemical reactions.

PubMed

Antillon, Edwin; Strachan, Alejandro

2015-02-28

We use a particle-based mesoscale model that incorporates chemical reactions at a coarse-grained level to study the response of materials that undergo volume-reducing chemical reactions under shockwave-loading conditions. We find that such chemical reactions can attenuate the shockwave and characterize how the parameters of the chemical model affect this behavior. The simulations show that the magnitude of the volume collapse and velocity at which the chemistry propagates are critical to weaken the shock, whereas the energetics in the reactions play only a minor role. Shock loading results in transient states where the material is away from local equilibrium and, interestingly, chemical reactions can nucleate under such non-equilibrium states. Thus, the timescales for equilibration between the various degrees of freedom in the material affect the shock-induced chemistry and its ability to attenuate the propagating shock.

Chain-reaction crash on a highway in high visibility

NASA Astrophysics Data System (ADS)

Nagatani, Takashi

2016-05-01

We study the chain-reaction crash (multiple-vehicle collision) in high-visibility condition on a highway. In the traffic situation, drivers control their vehicles by both gear-changing and braking. Drivers change the gears according to the headway and brake according to taillights of the forward vehicle. We investigate whether or not the first collision induces the chain-reaction crash numerically. It is shown that dynamic transitions occur from no collisions, through a single collision, to multiple collisions with decreasing the headway. Also, we find that the dynamic transition occurs from the finite chain reaction to the infinite chain reaction when the headway is less than the critical value. We compare the multiple-vehicle collisions in high-visibility with that in low-visibility. We derive the transition points and the region maps for the chain-reaction crash in high visibility.

Facet-Dependent Oxidative Goethite Growth As a Function of Aqueous Solution Conditions.

PubMed

Strehlau, Jennifer H; Stemig, Melissa S; Penn, R Lee; Arnold, William A

2016-10-04

Nitroaromatic compounds are groundwater pollutants that can be degraded through reactions with Fe(II) adsorbed on iron oxide nanoparticles, although little is known about the evolving reactivity of the minerals with continuous pollutant exposure. In this work, Fe(II)/goethite reactivity toward 4-chloronitrobenzene (4-ClNB) as a function of pH, organic matter presence, and reactant concentrations was explored using sequential-spike batch reactors. Reaction rate constants were smaller with lower pH, introduction of organic matter, and diluted reactant concentrations as compared to a reference condition. Reaction rate constants did not change with the number of 4-ClNB spikes for all reaction conditions. Under all conditions, oxidative goethite growth was demonstrated through X-ray diffraction, magnetic characterization, and transmission electron microscopy. Nonparametric statistics were applied to compare histograms of lengths and widths of goethite nanoparticles as a function of varied solution conditions. The conditions that slowed the reaction also resulted in statistically shorter and wider particles than for the faster reactions. Additionally, added organic matter interfered with particle growth on the favorable {021} faces to a greater extent, with statistically reduced rate of growth on the tip facets and increased rate of growth on the side facets. These data demonstrate that oxidative growth of goethite in aqueous systems is dependent on major groundwater variables, such as pH and the presence of organic matter, which could lead to the evolving reactivity of goethite particles in natural environments.

Flow chemistry kinetic studies reveal reaction conditions for ready access to unsymmetrical trehalose analogues.

PubMed

Patel, Mitul K; Davis, Benjamin G

2010-10-07

Monofunctionalization of trehalose, a widely-found symmetric plant disaccharide, was studied in a microreactor to give valuable kinetic insights that have allowed improvements in desymmetrization yields and the development of a reaction sequence for large scale monofunctionalizations that allow access to probes of trehalose's biological function.

Double Reformatsky reaction: divergent synthesis of δ-hydroxy-β-ketoesters.

PubMed

Mineno, Masahiro; Sawai, Yasuhiro; Kanno, Kazuaki; Sawada, Naotaka; Mizufune, Hideya

2013-06-21

The double Reformatsky reaction, tandem addition of two molecules of zinc alkanoate to a carbonyl compound, and its synthetic application to a series of δ-hydroxy-β-ketoesters has been developed. The key to accelerate the double Reformatsky reaction is considered to be a complex-induced proximity effect of the in situ generated zinc alkoxide coordinated with the pyridyl group of the substrate or bidentate amines. A noteworthy feature of the reaction system is its high tolerance of functional groups due to the moderate nucleophilicity of organozinc reagents and the mild reaction conditions. Moreover, spectroscopic and crystallographic analyses of the zinc complex of the double Reformatsky product support the proposed mechanism of reaction site discrimination for ketones, aldehydes, nitriles, carboxylic acid anhydrides, and esters.

Reaction of Titanium and Zirconium Particles in Cylindrical Explosive Charges

NASA Astrophysics Data System (ADS)

Frost, David; Cairns, Malcolm; Goroshin, Samuel; Zhang, Fan

2007-06-01

The critical conditions for the reaction of high melting-point metallic particles (Ti, Zr) dispersed during the detonation of long cylindrical explosive charges have been investigated experimentally. The charges consisted of packed beds of either spherical titanium particles (with diameters of 35, 90, or 215 μm; AP&C, Inc.) or nonspherical zirconium particles (250 -- 500 μm or 500 -- 600 μm, Atlantic Equipment Eng., NJ) saturated with sensitized liquid nitromethane. For the titanium particles, a threshold particle diameter exists, above which self-sustained particle reaction is not observed, although some particle reaction occurs immediately behind the detonation front then rapidly quenches. For the smallest particles, the proportion of the conical particle cloud that reacts increases with charge diameter, suggesting that the reaction initiation is a competition between particle heating and expansion cooling of the products. For zirconium particles, no critical conditions exist; particle ignition was observed for all particle and charge diameters tested. In this case, interaction of the high pressure detonation wave with the particles is sufficient to initiate reaction at the particle surface after a delay time (˜ 10's μs), which is much less than the time required for thermal equilibration of the particles.

A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reaction flows

NASA Technical Reports Server (NTRS)

Magnotti, F.; Diskin, G.; Matulaitis, J.; Chinitz, W.

1984-01-01

The use of silane (SiH4) as an effective ignitor and flame stabilizing pilot fuel is well documented. A reliable chemical kinetic mechanism for prediction of its behavior at the conditions encountered in the combustor of a SCRAMJET engine was calculated. The effects of hydrogen addition on hydrocarbon ignition and flame stabilization as a means for reduction of lengthy ignition delays and reaction times were studied. The ranges of applicability of chemical kinetic models of hydrogen-air combustors were also investigated. The CHARNAL computer code was applied to the turbulent reaction rate modeling.

Palladium-Catalyzed α-Arylation of Zinc Enolates of Esters: Reaction Conditions and Substrate Scope

PubMed Central

Hama, Takuo; Ge, Shaozhong; Hartwig, John F.

2013-01-01

The intermolecular α-arylation of esters by palladium-catalyzed coupling of aryl bromides with zinc enolates of esters is reported. Reactions of three different types of zinc enolates have been developed. α-Arylation of esters occurs in high yields with isolated Reformatsky reagents, with Reformatsky reagents generated from α-bromo esters and activated zinc, and with zinc enolates generated by quenching lithium enolates of esters with zinc chloride. The use of zinc enolates, instead of alkali metal enolates, greatly expands the scope of the arylation of esters. The reactions occur at room temperature or at 70 °C with bromoarenes containing cyano, nitro, ester, keto, fluoro, enolizable hydrogen, hydroxyl or amino functionality and with bromopyridines. The scope of esters encompasses acyclic acetates, propionates, and isobutyrates, α-alkoxyesters, and lactones. The arylation of zinc enolates of esters was conducted with catalysts bearing the hindered pentaphenylferrocenyl di-tert-butylphosphine (Q-phos) or the highly reactive dimeric Pd(I) complex {[P(t-Bu)3]PdBr}2. PMID:23931445

The Sugar Model: Autocatalytic Activity of the Triose-Ammonia Reaction

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

2006-01-01

Reaction of triose sugars with ammonia under anaerobic conditions yielded autocatalytic products. The autocatalytic behavior of the products was examined by measuring the effect of the crude triose-ammonia reaction product on the kinetics of a second identical triose-ammonia reaction. The reaction product showed autocatalytic activity by increasing both the rate of disappearance of triose and the rate formation of pyruvaldehyde, the product of triose dehydration. This synthetic process is considered a reasonable model of origin-of-life chemistry because it uses plausible prebiotic substrates, and resembles modern biosynthesis by employing the energized carbon groups of sugars to drive the synthesis of autocatalytic molecules.

Kinugasa reactions in water: from green chemistry to bioorthogonal labelling.

PubMed

Chigrinova, Mariya; MacKenzie, Douglas A; Sherratt, Allison R; Cheung, Lawrence L W; Pezacki, John Paul; Pezacki, Paul

2015-04-16

The Kinugasa reaction has become an efficient method for the direct synthesis of β-lactams from substituted nitrones and copper(I) acetylides. In recent years, the reaction scope has been expanded to include the use of water as the solvent, and with micelle-promoted [3+2] cycloadditions followed by rearrangement furnishing high yields of β-lactams. The high yields of stable products under aqueous conditions render the modified Kinugasa reaction amenable to metabolic labelling and bioorthogonal applications. Herein, the development of methods for use of the Kinugasa reaction in aqueous media is reviewed, with emphasis on its potential use as a bioorthogonal coupling strategy.

The Sugar Model: Autocatalytic Activity of the Triose Ammonia Reaction

NASA Astrophysics Data System (ADS)

Weber, Arthur L.

2007-04-01

Reaction of triose sugars with ammonia under anaerobic conditions yielded autocatalytic products. The autocatalytic behavior of the products was examined by measuring the effect of the crude triose ammonia reaction product on the kinetics of a second identical triose ammonia reaction. The reaction product showed autocatalytic activity by increasing both the rate of disappearance of triose and the rate of formation of pyruvaldehyde, the product of triose dehydration. This synthetic process is considered a reasonable model of origin-of-life chemistry because it uses plausible prebiotic substrates, and resembles modern biosynthesis by employing the energized carbon groups of sugars to drive the synthesis of autocatalytic molecules.

Mixing-dependent Reactions in the Hyporheic Zone: Laboratory and Numerical Experiments

NASA Astrophysics Data System (ADS)

Santizo, K. Y.; Eastes, L. A.; Hester, E. T.; Widdowson, M.

2017-12-01

The hyporheic zone is the surface water-groundwater interface surrounding the river's perimeter. Prior research demonstrates the ability of the hyporheic zone to attenuate pollutants when surface water cycles through reactive sediments (non-mixing-dependent reactions). However, the colocation of both surface and ground water within hyporheic sediments also allows mixing-dependent reactions that require mixing of reactants from these two water sources. Recent modeling studies show these mixing zones can be small under steady state homogeneous conditions, but do not validate those results in the laboratory or explore the range of hydrological characteristics that control the extent of mixing. Our objective was to simulate the mixing zone, quantify its thickness, and probe its hydrological controls using a "mix" of laboratory and numerical experiments. For the lab experiments, a hyporheic zone was simulated in a sand mesocosm, and a mixing-dependent abiotic reaction of sodium sulfite and dissolved oxygen was induced. Oxygen concentration response and oxygen consumption were visualized via planar optodes. Sulfate production by the mixing-dependent reaction was measured by fluid samples and a spectrophometer. Key hydrologic controls varied in the mesocosm included head gradient driving hyporheic exchange and hydraulic conductivity/heterogeneity. Results show a clear mixing area, sulfate production, and oxygen gradient. Mixing zone length (hyporheic flow cell size) and thickness both increase with the driving head gradient. For the numerical experiments, transient surface water boundary conditions were implemented together with heterogeneity of hydraulic conductivity. Results indicate that both fluctuating boundary conditions and heterogeneity increase mixing-dependent reaction. The hyporheic zone is deemed an attenuation hotspot by multiple studies, but here we demonstrate its potential for mixing-dependent reactions and the influence of important hydrological

Standard Gibbs energy of metabolic reactions: II. Glucose-6-phosphatase reaction and ATP hydrolysis.

PubMed

Meurer, Florian; Do, Hoang Tam; Sadowski, Gabriele; Held, Christoph

2017-04-01

ATP (adenosine triphosphate) is a key reaction for metabolism. Tools from systems biology require standard reaction data in order to predict metabolic pathways accurately. However, literature values for standard Gibbs energy of ATP hydrolysis are highly uncertain and differ strongly from each other. Further, such data usually neglect the activity coefficients of reacting agents, and published data like this is apparent (condition-dependent) data instead of activity-based standard data. In this work a consistent value for the standard Gibbs energy of ATP hydrolysis was determined. The activity coefficients of reacting agents were modeled with electrolyte Perturbed-Chain Statistical Associating Fluid Theory (ePC-SAFT). The Gibbs energy of ATP hydrolysis was calculated by combining the standard Gibbs energies of hexokinase reaction and of glucose-6-phosphate hydrolysis. While the standard Gibbs energy of hexokinase reaction was taken from previous work, standard Gibbs energy of glucose-6-phosphate hydrolysis reaction was determined in this work. For this purpose, reaction equilibrium molalities of reacting agents were measured at pH7 and pH8 at 298.15K at varying initial reacting agent molalities. The corresponding activity coefficients at experimental equilibrium molalities were predicted with ePC-SAFT yielding the Gibbs energy of glucose-6-phosphate hydrolysis of -13.72±0.75kJ·mol -1 . Combined with the value for hexokinase, the standard Gibbs energy of ATP hydrolysis was finally found to be -31.55±1.27kJ·mol -1 . For both, ATP hydrolysis and glucose-6-phosphate hydrolysis, a good agreement with own and literature values were obtained when influences of pH, temperature, and activity coefficients were explicitly taken into account in order to calculate standard Gibbs energy at pH7, 298.15K and standard state. Copyright © 2017 Elsevier B.V. All rights reserved.

Energy and molecules from photochemical/photocatalytic reactions. An overview.

PubMed

Ravelli, Davide; Protti, Stefano; Albini, Angelo

2015-01-16

Photocatalytic reactions have been defined as those processes that require both a (not consumed) catalyst and light. A previous definition was whether such reactions brought a system towards or away from the (thermal) equilibrium. This consideration brings in the question whether a part of the photon energy is incorporated into the photochemical reaction products. Data are provided for representative organic reactions involving or not molecular catalysts and show that energy storage occurs only when a heavily strained structure is generated, and in that case only a minor part of photon energy is actually stored (ΔG up to 25 kcal·mol-1). The green role of photochemistry/photocatalysis is rather that of forming highly reactive intermediates under mild conditions.

Theoretical verification of nonthermal microwave effects on intramolecular reactions.

PubMed

Kanno, Manabu; Nakamura, Kosuke; Kanai, Eri; Hoki, Kunihito; Kono, Hirohiko; Tanaka, Motohiko

2012-03-08

There have been a growing number of articles that report dramatic improvements in the experimental performance of chemical reactions by microwave irradiation compared to that under conventional heating conditions. We theoretically examined whether nonthermal microwave effects on intramolecular reactions exist or not, in particular, on Newman-Kwart rearrangements and intramolecular Diels-Alder reactions. The reaction rates of the former calculated by the transition state theory, which consider only the thermal effects of microwaves, agree quantitatively with experimental data, and thus, the increases in reaction rates can be ascribed to dielectric heating of the solvent by microwaves. In contrast, for the latter, the temperature dependence of reaction rates can be explained qualitatively by thermal effects but the possibility of nonthermal effects still remains regardless of whether competitive processes are present or not. The effective intramolecular potential energy surface in the presence of a microwave field suggests that nonthermal effects arising from potential distortion are vanishingly small in intramolecular reactions. It is useful in the elucidation of the reaction mechanisms of microwave synthesis to apply the present theoretical approach with reference to the experiments where thermal and nonthermal effects are separated by screening microwave fields.

Protease-catalysed Direct Asymmetric Mannich Reaction in Organic Solvent

NASA Astrophysics Data System (ADS)

Xue, Yang; Li, Ling-Po; He, Yan-Hong; Guan, Zhi

2012-10-01

We reported the first enzyme-catalysed, direct, three-component asymmetric Mannich reaction using protease type XIV from Streptomyces griseus (SGP) in acetonitrile. Yields of up to 92% with enantioselectivities of up to 88% e.e. and diastereoselectivities of up to 92:8 (syn:anti) were achieved under the optimised conditions. This enzyme's catalytic promiscuity expands the application of this biocatalyst and provides a potential alternative method for asymmetric Mannich reactions.

Force approach to radiation reaction

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

López, Gustavo V., E-mail: gulopez@udgserv.cencar.udg.mx

The difficulty of the usual approach to deal with the radiation reaction is pointed out, and under the condition that the radiation force must be a function of the external force and is zero whenever the external force be zero, a new and straightforward approach to radiation reaction force and damping is proposed. Starting from the Larmor formula for the power radiated by an accelerated charged particle, written in terms of the applied force instead of the acceleration, an expression for the radiation force is established in general, and applied to the examples for the linear and circular motion ofmore » a charged particle. This expression is quadratic in the magnitude of the applied force, inversely proportional to the speed of the charged particle, and directed opposite to the velocity vector. This force approach may contribute to the solution of the very old problem of incorporating the radiation reaction to the motion of the charged particles, and future experiments may tell us whether or not this approach point is in the right direction.« less

Parametric spatiotemporal oscillation in reaction-diffusion systems

NASA Astrophysics Data System (ADS)

Ghosh, Shyamolina; Ray, Deb Shankar

2016-03-01

We consider a reaction-diffusion system in a homogeneous stable steady state. On perturbation by a time-dependent sinusoidal forcing of a suitable scaling parameter the system exhibits parametric spatiotemporal instability beyond a critical threshold frequency. We have formulated a general scheme to calculate the threshold condition for oscillation and the range of unstable spatial modes lying within a V-shaped region reminiscent of Arnold's tongue. Full numerical simulations show that depending on the specificity of nonlinearity of the models, the instability may result in time-periodic stationary patterns in the form of standing clusters or spatially localized breathing patterns with characteristic wavelengths. Our theoretical analysis of the parametric oscillation in reaction-diffusion system is corroborated by full numerical simulation of two well-known chemical dynamical models: chlorite-iodine-malonic acid and Briggs-Rauscher reactions.

Parametric spatiotemporal oscillation in reaction-diffusion systems.

PubMed

Ghosh, Shyamolina; Ray, Deb Shankar

2016-03-01

We consider a reaction-diffusion system in a homogeneous stable steady state. On perturbation by a time-dependent sinusoidal forcing of a suitable scaling parameter the system exhibits parametric spatiotemporal instability beyond a critical threshold frequency. We have formulated a general scheme to calculate the threshold condition for oscillation and the range of unstable spatial modes lying within a V-shaped region reminiscent of Arnold's tongue. Full numerical simulations show that depending on the specificity of nonlinearity of the models, the instability may result in time-periodic stationary patterns in the form of standing clusters or spatially localized breathing patterns with characteristic wavelengths. Our theoretical analysis of the parametric oscillation in reaction-diffusion system is corroborated by full numerical simulation of two well-known chemical dynamical models: chlorite-iodine-malonic acid and Briggs-Rauscher reactions.

Effective Analysis of Reaction Time Data

ERIC Educational Resources Information Center

Whelan, Robert

2008-01-01

Most analyses of reaction time (RT) data are conducted by using the statistical techniques with which psychologists are most familiar, such as analysis of variance on the sample mean. Unfortunately, these methods are usually inappropriate for RT data, because they have little power to detect genuine differences in RT between conditions. In…

Investigation of the reactions of skin panels in relation to duration of acoustical loading

NASA Technical Reports Server (NTRS)

Kvitka, V. Y.; Kernes, G. I.

1973-01-01

Certain characteristics of the reactions of typical skin panels of a passenger aircraft to acoustical loading are being investigated, for development of an objective method of diagnostics for skin condition, under the operations and maintenance sections of civil aviation. There are a number of difficulties connected with the solution of this problem. The reactions of skin panels exposed to the noises of the exhaust jets are dependent on the aircraft operating conditions, the geometric parameters and limiting conditions of the panels.

Reaction rate for carbon burning in massive stars

NASA Astrophysics Data System (ADS)

Jiang, C. L.; Santiago-Gonzalez, D.; Almaraz-Calderon, S.; Rehm, K. E.; Back, B. B.; Auranen, K.; Avila, M. L.; Ayangeakaa, A. D.; Bottoni, S.; Carpenter, M. P.; Dickerson, C.; DiGiovine, B.; Greene, J. P.; Hoffman, C. R.; Janssens, R. V. F.; Kay, B. P.; Kuvin, S. A.; Lauritsen, T.; Pardo, R. C.; Sethi, J.; Seweryniak, D.; Talwar, R.; Ugalde, C.; Zhu, S.; Bourgin, D.; Courtin, S.; Haas, F.; Heine, M.; Fruet, G.; Montanari, D.; Jenkins, D. G.; Morris, L.; Lefebvre-Schuhl, A.; Alcorta, M.; Fang, X.; Tang, X. D.; Bucher, B.; Deibel, C. M.; Marley, S. T.

2018-01-01

Carbon burning is a critical phase for nucleosynthesis in massive stars. The conditions for igniting this burning stage, and the subsequent isotope composition of the resulting ashes, depend strongly on the reaction rate for 12C+12C fusion at very low energies. Results for the cross sections for this reaction are influenced by various backgrounds encountered in measurements at such energies. In this paper, we report on a new measurement of 12C+12C fusion cross sections where these backgrounds have been minimized. It is found that the astrophysical S factor exhibits a maximum around Ecm=3.5 -4.0 MeV, which leads to a reduction of the previously predicted astrophysical reaction rate.

Allergic reaction to polyethylene glycol in a painter.

PubMed

Antolin-Amerigo, D; Sánchez-González, M J; Barbarroja-Escudero, J; Rodríguez-Rodríguez, M; Álvarez-Perea, A; Alvarez-Mon, M

2015-08-01

We report a case of a male painter who visited our outpatient clinic after developing a distinct skin reaction 15 min after the ingestion of a laxative solution containing polyethylene glycol (PEG) prior to colonoscopy. He described suffering from the same skin reaction when he was previously exposed to paints that contained PEG-4000. An exposure challenge test with pure PEG-4000, simulating his workplace conditions, elicited a generalized urticarial reaction. Allergy to PEG should be considered in painters who develop urticarial or other systemic symptoms after handling PEG-containing products. © The Author 2015. Published by Oxford University Press on behalf of the Society of Occupational Medicine. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Synthesis Under 'Greener' Conditions: Role of Sustainable Nano-Catalysts

EPA Science Inventory

The presentation summarizes our recent activity in chemical synthesis involving benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions.1 The synthesis of heterocyclic compounds, coupling reactions, and a varie...

Combinatorial Partial Hydrogenation Reactions of 4-Nitroacetophenone: An Undergraduate Organic Laboratory

ERIC Educational Resources Information Center

Kittredge, Kevin W.; Marine, Susan S.; Taylor, Richard T.

2004-01-01

A molecule possessing other functional groups that could be hydrogenerated is examined, where a variety of metal catalysts are evaluated under similar reaction conditions. Optimizing organic reactions is both time and labor intensive, and the use of a combinatorial parallel synthesis reactor was great time saving device, as per summary.

Propensity approach to nonequilibrium thermodynamics of a chemical reaction network: Controlling single E-coli β-galactosidase enzyme catalysis through the elementary reaction stepsa)

NASA Astrophysics Data System (ADS)

Das, Biswajit; Banerjee, Kinshuk; Gangopadhyay, Gautam

2013-12-01

In this work, we develop an approach to nonequilibrium thermodynamics of an open chemical reaction network in terms of the elementary reaction propensities. The method is akin to the microscopic formulation of the dissipation function in terms of the Kullback-Leibler distance of phase space trajectories in Hamiltonian system. The formalism is applied to a single oligomeric enzyme kinetics at chemiostatic condition that leads the reaction system to a nonequilibrium steady state, characterized by a positive total entropy production rate. Analytical expressions are derived, relating the individual reaction contributions towards the total entropy production rate with experimentally measurable reaction velocity. Taking a real case of Escherichia coli β-galactosidase enzyme obeying Michaelis-Menten kinetics, we thoroughly analyze the temporal as well as the steady state behavior of various thermodynamic quantities for each elementary reaction. This gives a useful insight in the relative magnitudes of various energy terms and the dissipated heat to sustain a steady state of the reaction system operating far-from-equilibrium. It is also observed that, the reaction is entropy-driven at low substrate concentration and becomes energy-driven as the substrate concentration rises.

Formation of Acetylene in the Reaction of Methane with Iron Carbide Cluster Anions FeC3- under High-Temperature Conditions.

PubMed

Li, Hai-Fang; Jiang, Li-Xue; Zhao, Yan-Xia; Liu, Qing-Yu; Zhang, Ting; He, Sheng-Gui

2018-03-01

The underlying mechanism for non-oxidative methane aromatization remains controversial owing to the lack of experimental evidence for the formation of the first C-C bond. For the first time, the elementary reaction of methane with atomic clusters (FeC 3 - ) under high-temperature conditions to produce C-C coupling products has been characterized by mass spectrometry. With the elevation of temperature from 300 K to 610 K, the production of acetylene, the important intermediate proposed in a monofunctional mechanism of methane aromatization, was significantly enhanced, which can be well-rationalized by quantum chemistry calculations. This study narrows the gap between gas-phase and condensed-phase studies on methane conversion and suggests that the monofunctional mechanism probably operates in non-oxidative methane aromatization. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Reaction between Iron(II) Iodide and Potassium Dichromate(VI) in Acidified Aqueous Solution

ERIC Educational Resources Information Center

Talbot, Christopher

2013-01-01

This "Science note" teaching lesson explores the possible reaction between the ions in a reaction mixture consisting of iron(II) iodide and potassium dichromate(VI) in acidified aqueous solution. The electrode potentials will be used to deduce any spontaneous reactions under standard thermodynamic conditions (298 K, 1 bar (approximately…

Microwave-Assisted Organic Synthesis in the Organic Teaching Lab: A Simple, Greener Wittig Reaction

ERIC Educational Resources Information Center

Martin, Eric; Kellen-Yuen, Cynthia

2007-01-01

A greener, microwave-assisted Wittig reaction has been developed for the second-semester organic teaching laboratory. Utilizing this microwave technique, a variety of styrene derivatives have been successfully synthesized from aromatic aldehydes in good yields (41-68%). The reaction not only occurs under neat reaction conditions, but also employs…

An integrated open framework for thermodynamics of reactions that combines accuracy and coverage.

PubMed

Noor, Elad; Bar-Even, Arren; Flamholz, Avi; Lubling, Yaniv; Davidi, Dan; Milo, Ron

2012-08-01

The laws of thermodynamics describe a direct, quantitative relationship between metabolite concentrations and reaction directionality. Despite great efforts, thermodynamic data suffer from limited coverage, scattered accessibility and non-standard annotations. We present a framework for unifying thermodynamic data from multiple sources and demonstrate two new techniques for extrapolating the Gibbs energies of unmeasured reactions and conditions. Both methods account for changes in cellular conditions (pH, ionic strength, etc.) by using linear regression over the ΔG(○) of pseudoisomers and reactions. The Pseudoisomeric Reactant Contribution method systematically infers compound formation energies using measured K' and pK(a) data. The Pseudoisomeric Group Contribution method extends the group contribution method and achieves a high coverage of unmeasured reactions. We define a continuous index that predicts the reversibility of a reaction under a given physiological concentration range. In the characteristic physiological range 3μM-3mM, we find that roughly half of the reactions in Escherichia coli's metabolism are reversible. These new tools can increase the accuracy of thermodynamic-based models, especially in non-standard pH and ionic strengths. The reversibility index can help modelers decide which reactions are reversible in physiological conditions. Freely available on the web at: http://equilibrator.weizmann.ac.il. Website implemented in Python, MySQL, Apache and Django, with all major browsers supported. The framework is open-source (code.google.com/p/milo-lab), implemented in pure Python and tested mainly on Linux. ron.milo@weizmann.ac.il Supplementary data are available at Bioinformatics online.

An integrated open framework for thermodynamics of reactions that combines accuracy and coverage

PubMed Central

Noor, Elad; Bar-Even, Arren; Flamholz, Avi; Lubling, Yaniv; Davidi, Dan; Milo, Ron

2012-01-01

Motivation: The laws of thermodynamics describe a direct, quantitative relationship between metabolite concentrations and reaction directionality. Despite great efforts, thermodynamic data suffer from limited coverage, scattered accessibility and non-standard annotations. We present a framework for unifying thermodynamic data from multiple sources and demonstrate two new techniques for extrapolating the Gibbs energies of unmeasured reactions and conditions. Results: Both methods account for changes in cellular conditions (pH, ionic strength, etc.) by using linear regression over the ΔG○ of pseudoisomers and reactions. The Pseudoisomeric Reactant Contribution method systematically infers compound formation energies using measured K′ and pKa data. The Pseudoisomeric Group Contribution method extends the group contribution method and achieves a high coverage of unmeasured reactions. We define a continuous index that predicts the reversibility of a reaction under a given physiological concentration range. In the characteristic physiological range 3μM–3mM, we find that roughly half of the reactions in Escherichia coli's metabolism are reversible. These new tools can increase the accuracy of thermodynamic-based models, especially in non-standard pH and ionic strengths. The reversibility index can help modelers decide which reactions are reversible in physiological conditions. Availability: Freely available on the web at: http://equilibrator.weizmann.ac.il. Website implemented in Python, MySQL, Apache and Django, with all major browsers supported. The framework is open-source (code.google.com/p/milo-lab), implemented in pure Python and tested mainly on Linux. Contact: ron.milo@weizmann.ac.il Supplementary Information: Supplementary data are available at Bioinformatics online. PMID:22645166

Microwave assisted IMDAF# reaction: microwave irradiation applied with success to cycloaddition reaction of N-propargyl-N-p-tolyl-N-2-furfurylamines.

PubMed

Mance, Ana Dunja; Jakopcić, Kresimir

2005-01-01

The new tertiary furfurylamine with triple bond as a dienophylic part i.e. N-(5-methyl-2-furfuryl)-N-prop-2-ynyl-p-toluidine (1) was prepared and the intramolecular Diels-Alder reaction of the amine (1) was performed under microwave irradiation conditions and by heating a benzene solution of the amine under nitrogen. Comparing the results of the usual thermal and the MAOS reaction, we confirmed our expectations that MAOS could promote the outcome of IMDA reaction of the suitably N-substituted tertiary 2-furfuryl-amines. In the present example, N-p-tolyl-5-methyl-5,7a-dihydro-5,7a-epoxyisoindoline was obtained in much better yield and of higher purity.

Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with Alcohols via C-S Bond Cleavage: Reaction Development and Mechanism Study.

PubMed

Du, Bingnan; Wang, Wenmin; Wang, Yang; Qi, Zhenghang; Tian, Jiaqi; Zhou, Jie; Wang, Xiaochen; Han, Jianlin; Ma, Jing; Pan, Yi

2018-02-16

A Cu-catalyzed cascade oxidative radical process of β-keto sulfones with alcohols has been achieved by using oxygen as an oxidant. In this reaction, β-keto sulfones were converted into sulfinate esters under the oxidative conditions via cleavage of C-S bond. Experimental and computational studies demonstrate that a new pathway is involved in this reaction, which proceeds through the formation of the key four-coordinated Cu II intermediate, O-O bond homolysis induced C-S bond cleavage and Cu-catalyzed esterification to form the final products. This reaction provides a new strategy to sulfonate esters and enriches the research content of C-S bond cleavage and transformations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The impact of raw materials and baking conditions on Maillard reaction products, thiamine, folate, phytic acid and minerals in white bread.

PubMed

Helou, Cynthia; Gadonna-Widehem, Pascale; Robert, Nathalie; Branlard, Gérard; Thebault, Jacques; Librere, Sarah; Jacquot, Sylvain; Mardon, Julie; Piquet-Pissaloux, Agnès; Chapron, Sophie; Chatillon, Antoine; Niquet-Léridon, Céline; Tessier, Frédéric J

2016-06-15

The aim of this study was to develop a white bread with improved nutrient contents and reduced levels of potentially harmful Maillard reaction products such as N(ε)-carboxymethyllysine (CML) and 5-hydroxymethylfurfural (HMF). Assays were carried out through a full factorial experimental design allowing the simultaneous analysis of four factors at two levels: (1) wheat flour extraction rates (ash content: 0.60%-0.72%), (2) leavening agents (bakers' yeast - bakers' yeast and sourdough), (3) prebaking and (4) baking conditions (different sets of time and temperature). The baking conditions affected HMF and CML as well as certain mineral contents. A reduced baking temperature along with a prolonged heat treatment was found to be favourable for reducing both the CML (up to 20%) and HMF concentrations (up to 96%). The presence of sourdough decreased the formation of CML (up to 28%), and increased the apparent amounts of calcium (up to 8%) and manganese (up to 17.5%) probably through acidification of the dough. The extraction rate of flours as well as interactions between multiple factors also affected certain mineral content. However, compounds like folate, thiamine, copper, zinc, iron and phytic acid were not affected by any of the factors studied.

Ethanol Conversion to Hydrocarbons on HZSM-5: Effect of Reaction Conditions and Si/Al Ratio on the Product Distributions

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

Ramasamy, Karthikeyan K.; Wang, Yong

2014-11-17

The Conversion of ethanol to hydrocarbon over HZSM-5 zeolite with different Si/Al ratios was investigated under various reaction conditions. The catalyst with a higher Si/Al ratio (low acid density) deactivated faster and generated more unsaturated compounds at a similar time-on-stream. Temperature affects the catalytic activity with respect to liquid hydrocarbon generation and the hydrocarbon product composition. At lower temperatures (~300°C), the catalyst deactivated faster with respect to the liquid hydrocarbon formation. Higher temperatures (~400°C) reduced the formation of liquid range hydrocarbons and formed more gaseous fractions. Weight hourly space velocity was also found to affect product selectivity with higher weightmore » hourly space velocity leading to a higher extent of ethylene formation. The experimental results were analyzed in terms of the product composition and the coke content with respect to catalyst time-on-stream and compared with the catalyst lifetime with respect to the variables tested on the conversion of ethanol to hydrocarbon.« less

Effect of pepper lipoxygenase activity and its linked reactions on pigments of the pepper fruit.

PubMed

Jarén-Galán, M; Mínguez-Mosquera, M I

1999-11-01

The products formed during the enzymatic reaction catalyzed by the lipoxygenase of pepper (variety Agridulce) have in vitro a strong destructive action on the carotenoid pigments of the fruit. When conditions and proportions of enzyme and pigments are similar to those found in the fruit, and at a reaction temperature of 20 degrees C, almost 30% of the pigments are destroyed after 24 h of reaction. Of this amount, 2.5% is due to autoxidation of pigments, 4. 5% to oxidation induced by the presence of linoleic under saturating conditions, and the remaining 22% to the presence in the medium of reaction products of the lipoxygenase-catalyzed reaction. When the enzyme acts under substrate-saturating conditions, the rate of pigment destruction by lipoxygenase can be considered maximal at the experimental temperature. The fact that in vitro pepper lipoxygenase induces a heavy destruction of pigments and that, in vivo, its activity remains almost constant during over-ripening could explain why up to 40% of the pigment content in some varieties is lost during the postharvest period.

Recent developments in biocatalysis in multiphasic ionic liquid reaction systems.

PubMed

Meyer, Lars-Erik; von Langermann, Jan; Kragl, Udo

2018-06-01

Ionic liquids are well known and frequently used 'designer solvents' for biocatalytic reactions. This review highlights recent achievements in the field of multiphasic ionic liquid-based reaction concepts. It covers classical biphasic systems including supported ionic liquid phases, thermo-regulated multi-component solvent systems (TMS) and polymerized ionic liquids. These powerful concepts combine unique reaction conditions with a high potential for future applications on a laboratory and industrial scale. The presence of a multiphasic system simplifies downstream processing due to the distribution of the catalyst and reactants in different phases.

Development and application of bond cleavage reactions in bioorthogonal chemistry.

PubMed

Li, Jie; Chen, Peng R

2016-03-01

Bioorthogonal chemical reactions are a thriving area of chemical research in recent years as an unprecedented technique to dissect native biological processes through chemistry-enabled strategies. However, current concepts of bioorthogonal chemistry have largely centered on 'bond formation' reactions between two mutually reactive bioorthogonal handles. Recently, in a reverse strategy, a collection of 'bond cleavage' reactions has emerged with excellent biocompatibility. These reactions have expanded our bioorthogonal chemistry repertoire, enabling an array of exciting new biological applications that range from the chemically controlled spatial and temporal activation of intracellular proteins and small-molecule drugs to the direct manipulation of intact cells under physiological conditions. Here we highlight the development and applications of these bioorthogonal cleavage reactions. Furthermore, we lay out challenges and propose future directions along this appealing avenue of research.

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.

Eco-friendly polyethylene glycol promoted Michael addition reactions of α,β-unsaturated carbonyl compounds

EPA Science Inventory

Abstract- Intra- and inter-nucleophilic addition reactions of different unsaturated compounds were found to be highly effective without any additives in PEG-400 as a recyclable reaction medium under neutral conditions.

Forward design of a complex enzyme cascade reaction

PubMed Central

Hold, Christoph; Billerbeck, Sonja; Panke, Sven

2016-01-01

Enzymatic reaction networks are unique in that one can operate a large number of reactions under the same set of conditions concomitantly in one pot, but the nonlinear kinetics of the enzymes and the resulting system complexity have so far defeated rational design processes for the construction of such complex cascade reactions. Here we demonstrate the forward design of an in vitro 10-membered system using enzymes from highly regulated biological processes such as glycolysis. For this, we adapt the characterization of the biochemical system to the needs of classical engineering systems theory: we combine online mass spectrometry and continuous system operation to apply standard system theory input functions and to use the detailed dynamic system responses to parameterize a model of sufficient quality for forward design. This allows the facile optimization of a 10-enzyme cascade reaction for fine chemical production purposes. PMID:27677244

Prebiotic condensation reactions using cyanamide

NASA Technical Reports Server (NTRS)

Sherwood, E.; Nooner, D. W.; Eichberg, J.; Epps, D. E.; Oro, J.

1978-01-01

Condensation reactions in cyanamide, 4-amino-5-imidazole-carboxamide and cyanamide, imidazole systems under dehydrating conditions at moderate temperatures (60 to 100 deg C) were investigated. The cyanamide, imidazole system was used for synthesis of palmitoylglycerols from ammonium palmitate and glycerol. With the addition of deoxythymidine to the former system, P1, P2-dideoxythymidine 5 prime-phosphate was obtained; the same cyanamide, 4-amino-5-imidazole-carboxamide system was used to synthesize deoxythymidine oligonucleotides using deoxythymidine 5 prime-phosphate and deoxythymidine 5 prime-triphosphate, and peptides using glycine, phenylalanine or isoleucine with adenosine 5 prime-triphosphate. The pH requirements for these reactions make their prebiotic significance questionable; however, it is conceivable that they could occur in stable pockets of low interlayer acidity in a clay such as montmorillonite.

Solid catalyzed isoparaffin alkylation at supercritical fluid and near-supercritical fluid conditions

DOEpatents

Ginosar, Daniel M.; Fox, Robert V.; Kong, Peter C.

2000-01-01

This invention relates to an improved method for the alkylation reaction of isoparaffins with olefins over solid catalysts including contacting a mixture of an isoparaffin, an olefin and a phase-modifying material with a solid acid catalyst member under alkylation conversion conditions at either supercritical fluid, or near-supercritical fluid conditions, at a temperature and a pressure relative to the critical temperature(T.sub.c) and the critical pressure(P.sub.c) of the reaction mixture. The phase-modifying phase-modifying material is employed to promote the reaction's achievement of either a supercritical fluid state or a near-supercritical state while simultaneously allowing for decreased reaction temperature and longer catalyst life.

Single-molecule stochastic times in a reversible bimolecular reaction

NASA Astrophysics Data System (ADS)

Keller, Peter; Valleriani, Angelo

2012-08-01

In this work, we consider the reversible reaction between reactants of species A and B to form the product C. We consider this reaction as a prototype of many pseudobiomolecular reactions in biology, such as for instance molecular motors. We derive the exact probability density for the stochastic waiting time that a molecule of species A needs until the reaction with a molecule of species B takes place. We perform this computation taking fully into account the stochastic fluctuations in the number of molecules of species B. We show that at low numbers of participating molecules, the exact probability density differs from the exponential density derived by assuming the law of mass action. Finally, we discuss the condition of detailed balance in the exact stochastic and in the approximate treatment.

14 CFR 25.483 - One-gear landing conditions.

Code of Federal Regulations, 2010 CFR

2010-01-01

... conditions. For the one-gear landing conditions, the airplane is assumed to be in the level attitude and to... this attitude— (a) The ground reactions must be the same as those obtained on that side under § 25.479...

Green synthesis of Pd/CuO nanoparticles by Theobroma cacao L. seeds extract and their catalytic performance for the reduction of 4-nitrophenol and phosphine-free Heck coupling reaction under aerobic conditions.

PubMed

Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Rostami-Vartooni, Akbar; Bagherzadeh, Mojtaba

2015-06-15

We report the green synthesis of palladium/CuO nanoparticles (Pd/CuO NPs) using Theobroma cacao L. seeds extract and their catalytic activity for the reduction of 4-nitrophenol and Heck coupling reaction under aerobic conditions. The catalyst was characterized using the powder XRD, TEM, EDS, UV-vis and FT-IR. This method has the advantages of high yields, elimination of surfactant, ligand and homogeneous catalysts, simple methodology and easy work up. The catalyst can be recovered from the reaction mixture and reused several times without any significant loss of catalytic activity. Copyright © 2015 Elsevier Inc. All rights reserved.

DEPENDENCE OF X-RAY BURST MODELS ON NUCLEAR REACTION RATES

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

Cyburt, R. H.; Keek, L.; Schatz, H.

2016-10-20

X-ray bursts are thermonuclear flashes on the surface of accreting neutron stars, and reliable burst models are needed to interpret observations in terms of properties of the neutron star and the binary system. We investigate the dependence of X-ray burst models on uncertainties in (p, γ ), ( α , γ ), and ( α , p) nuclear reaction rates using fully self-consistent burst models that account for the feedbacks between changes in nuclear energy generation and changes in astrophysical conditions. A two-step approach first identified sensitive nuclear reaction rates in a single-zone model with ignition conditions chosen to matchmore » calculations with a state-of-the-art 1D multi-zone model based on the Kepler stellar evolution code. All relevant reaction rates on neutron-deficient isotopes up to mass 106 were individually varied by a factor of 100 up and down. Calculations of the 84 changes in reaction rate with the highest impact were then repeated in the 1D multi-zone model. We find a number of uncertain reaction rates that affect predictions of light curves and burst ashes significantly. The results provide insights into the nuclear processes that shape observables from X-ray bursts, and guidance for future nuclear physics work to reduce nuclear uncertainties in X-ray burst models.« less

Production of Furfural from Process-Relevant Biomass-Derived Pentoses in a Biphasic Reaction System

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

Mittal, Ashutosh; Black, Stuart K.; Vinzant, Todd B.

Furfural is an important fuel precursor which can be converted to hydrocarbon fuels and fuel intermediates. In this work, the production of furfural by dehydration of process-relevant pentose rich corn stover hydrolyzate using a biphasic batch reaction system has been investigated. Methyl isobutyl ketone (MIBK) and toluene have been used to extract furfural and enhance overall furfural yield by limiting its degradation to humins. The effects of reaction time, temperature, and acid concentration (H 2SO 4) on pentose conversion and furfural yield were investigated. For the dehydration of 8 wt % pentose-rich corn stover hydrolyzate under optimum reaction conditions, 0.05more » M H 2SO 4, 170 degrees C for 20 min with MIBK as the solvent, complete conversion of xylose (98-100%) and a furfural yield of 80% were obtained. Under these same conditions, except with toluene as the solvent, the furfural yield was 77%. Additionally, dehydration of process-relevant pentose rich corn stover hydrolyzate using solid acid ion-exchange resins under optimum reaction conditions has shown that Purolite CT275 is as effective as H 2SO 4 for obtaining furfural yields approaching 80% using a biphasic batch reaction system. In conclusion, this work has demonstrated that a biphasic reaction system can be used to process biomass-derived pentose rich sugar hydrolyzates to furfural in yields approaching 80%.« less

Production of Furfural from Process-Relevant Biomass-Derived Pentoses in a Biphasic Reaction System

DOE PAGES

Mittal, Ashutosh; Black, Stuart K.; Vinzant, Todd B.; ...

2017-05-16

Furfural is an important fuel precursor which can be converted to hydrocarbon fuels and fuel intermediates. In this work, the production of furfural by dehydration of process-relevant pentose rich corn stover hydrolyzate using a biphasic batch reaction system has been investigated. Methyl isobutyl ketone (MIBK) and toluene have been used to extract furfural and enhance overall furfural yield by limiting its degradation to humins. The effects of reaction time, temperature, and acid concentration (H 2SO 4) on pentose conversion and furfural yield were investigated. For the dehydration of 8 wt % pentose-rich corn stover hydrolyzate under optimum reaction conditions, 0.05more » M H 2SO 4, 170 degrees C for 20 min with MIBK as the solvent, complete conversion of xylose (98-100%) and a furfural yield of 80% were obtained. Under these same conditions, except with toluene as the solvent, the furfural yield was 77%. Additionally, dehydration of process-relevant pentose rich corn stover hydrolyzate using solid acid ion-exchange resins under optimum reaction conditions has shown that Purolite CT275 is as effective as H 2SO 4 for obtaining furfural yields approaching 80% using a biphasic batch reaction system. In conclusion, this work has demonstrated that a biphasic reaction system can be used to process biomass-derived pentose rich sugar hydrolyzates to furfural in yields approaching 80%.« less

Reaction rate for carbon burning in massive stars

DOE PAGES

Jiang, C. L.; Santiago-Gonzalez, D.; Almaraz-Calderon, S.; ...

2018-01-10

Carbon burning is a critical phase for nucleosynthesis in massive stars. The conditions for igniting this burning stage, and the subsequent isotope composition of the resulting ashes, depend strongly on the reaction rate for 12C+ 12C fusion at very low energies. Results for the cross sections for this reaction are influenced by various backgrounds encountered in measurements at such energies. In this paper, we report on a new measurement of 12C+ 12C fusion cross sections where these backgrounds have been minimized. In conclusion, it is found that the astrophysical S factor exhibits a maximum around E cm=3.5–4.0 MeV, which leadsmore » to a reduction of the previously predicted astrophysical reaction rate.« less

Variation in reaction norms: Statistical considerations and biological interpretation.

PubMed

Morrissey, Michael B; Liefting, Maartje

2016-09-01

Analysis of reaction norms, the functions by which the phenotype produced by a given genotype depends on the environment, is critical to studying many aspects of phenotypic evolution. Different techniques are available for quantifying different aspects of reaction norm variation. We examine what biological inferences can be drawn from some of the more readily applicable analyses for studying reaction norms. We adopt a strongly biologically motivated view, but draw on statistical theory to highlight strengths and drawbacks of different techniques. In particular, consideration of some formal statistical theory leads to revision of some recently, and forcefully, advocated opinions on reaction norm analysis. We clarify what simple analysis of the slope between mean phenotype in two environments can tell us about reaction norms, explore the conditions under which polynomial regression can provide robust inferences about reaction norm shape, and explore how different existing approaches may be used to draw inferences about variation in reaction norm shape. We show how mixed model-based approaches can provide more robust inferences than more commonly used multistep statistical approaches, and derive new metrics of the relative importance of variation in reaction norm intercepts, slopes, and curvatures. © 2016 The Author(s). Evolution © 2016 The Society for the Study of Evolution.

Citrus Peel Additives for One-Pot Triazole Formation by Decarboxylation, Nucleophilic Substitution, and Azide-Alkyne Cycloaddition Reactions

ERIC Educational Resources Information Center

Mendes, Desiree E.; Schoffstall, Allen M.

2011-01-01

This undergraduate organic laboratory experiment consists of three different reactions occurring in the same flask: a cycloaddition reaction, preceded by decarboxylation and nucleophilic substitution reactions. The decarboxylation and cycloaddition reactions occur using identical Cu(I) catalyst and conditions. Orange, lemon, and other citrus fruit…

Reaction-Mediated Desorption of Macromolecules: Novel Phenomenon Enabling Simultaneous Reaction and Separation.

PubMed

Isakari, Yu; Kishi, Yuhi; Yoshimoto, Noriko; Yamamoto, Shuichi; Podgornik, Aleš

2018-02-02

Combining chemical reaction with separation offers several advantages. In this work possibility to induce spontaneous desorption of adsorbed macromolecules, once being PEGylated, through adjustment of the reagent composition is investigated. Bovine serum albumin (BSA) and activated oligonucleotide, 9T, are used as the test molecules and 20 kDa linear activated PEG is used for their PEGylation. BSA solid-phase PEGylation is performed on Q Sepharose HP. Distribution coefficient of BSA and PEG-BSA as a function of NaCl is determined using linear gradient elution (LGE) experiments and Yamamoto model. According to the distribution coefficient the selectivity between BSA and PEG - BSA of around 15 is adjusted by using NaCl. Spontaneous desorption of PEG - BSA is detected with no presence of BSA. However, due to a rather low selectivity, also desorption of BSA occurred at high elution volume. A similar procedure is applied for activated 9T oligonucleotide, this time using monolithic CIM QA disk monolithic column for adsorption. Selectivity of over 2000 is obtained by proper adjustment of PEG reagent composition. High selectivity enables spontaneous desorption of PEG-9T without any desorption of activated 9T. Both experiments demonstrates that reaction-mediated desorption of macromolecules is possible when the reaction conditions are properly tuned. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effective prescribing in steroid allergy: controversies and cross-reactions.

PubMed

Browne, Fiona; Wilkinson, S Mark

2011-01-01

Contact allergy to topical corticosteroids should be considered in all patients who do not respond to, or are made worse by, the use of topical steroids. The incidence of steroid allergy in such patients is reported as 9% to 22% in adult patients and in 25% of children. It can often go undiagnosed for a long time in patients with a long history of dermatologic conditions and steroid use. Although rare, both immediate and delayed-type hypersensitivity reactions have been reported to systemic corticosteroids with an incidence of 0.3%. Reported reactions range from localized eczematous eruptions to systemic reactions, anaphylaxis, and even death. Delayed type reactions to systemically administered steroids may present as a generalized dermatitis, an exanthematous eruption, or occasionally, with blistering or purpura. In this contribution, we clarify the issues surrounding the pathogenesis of steroid allergy, cover the importance of cross-reactions, and describe strategies for the investigation and management for patients with suspected steroid allergy. Copyright © 2011 Elsevier Inc. All rights reserved.

Kinetics of OH + CO reaction under atmospheric conditions

NASA Technical Reports Server (NTRS)

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

1986-01-01

A pulsed laser photolysis-pulsed laser-induced fluorescence technique is used to directly measure the temperature, pressure, and H2O concentration dependence on k1 in air. K1 is found to increase linearly with increasing pressure at pressures of not greater than 1 atm, and the pressure dependence of k1 at 299 K is the same in N2 buffer gas as in O2 buffer gas. The rate constant in the low-pressure limit and the slope of the k1 versus pressure dependence are shown to be the same at 262 K as at 299 K. The present results significantly reduce the current atmospheric model uncertainties in the temperature dependence under atmospheric conditions, in the third body efficiency of O2, and in the effect of water vapor on k1.

Organic reactions catalyzed by methylrhenium trioxide: Reactions of ethyl diazoacetate and organic azides

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

Zhu, Z.; Espenson, J.H.

1996-10-16

Methylrhenium trioxide (CH{sub 3}ReO{sub 3} or MTO) catalyzes several classes of reactions of ethyl diazoacetate, EDA. It is the first high valent oxo complex for carbene transfer. Under mild conditions and in the absence of other substrates, EDA was converted to a 9:1 mixture of diethyl maleate and diethyl fumarate. In the presence of alcohols, {alpha}-alkoxy ethyl acetates were obtained in good yield. The yields dropped for the larger and more branched alcohols, the balance of material being diethyl maleate and fumarate. An electron-donating group in the para position of phenols favors the formation of {alpha}-phenoxy ethyl acetates. The usemore » of EDA to form {alpha}-thio ethyl acetates and N-substituted glycine ethyl esters, on the other hand, is hardly affected by the size or structure of the parent thiol or amine, with all of these reactions proceeding in high yield. MTO-catalyzed cycloaddition reactions occur between EDA and aromatic imines, olefins, and carbonyl compounds. Three-membered ring products are formed: aziridines, cyclopropanes, and epoxides, respectively. The reactions favor the formation of trans products, and provide a convenient route for the preparation of aziridines. Intermediate carbenoid and nitrenoid species have been proposed. In the presence of an oxygen source such as an epoxide, ethyl diazoacetate and azibenzil are converted to an oxalic acid monoethyl ester and to benzil; at the same time the epoxide was converted to an olefin. 75 refs., 1 fig., 7 tabs.« less

Unravelling Site-Specific Photo-Reactions of Ethanol on Rutile TiO2(110)

PubMed Central

Hansen, Jonas Ø.; Bebensee, Regine; Martinez, Umberto; Porsgaard, Soeren; Lira, Estephania; Wei, Yinying; Lammich, Lutz; Li, Zheshen; Idriss, Hicham; Besenbacher, Flemming; Hammer, Bjørk; Wendt, Stefan

2016-01-01

Finding the active sites of catalysts and photo-catalysts is crucial for an improved fundamental understanding and the development of efficient catalytic systems. Here we have studied the photo-activated dehydrogenation of ethanol on reduced and oxidized rutile TiO2(110) in ultrahigh vacuum conditions. Utilizing scanning tunnelling microscopy, various spectroscopic techniques and theoretical calculations we found that the photo-reaction proceeds most efficiently when the reactants are adsorbed on regular Ti surface sites, whereas species that are strongly adsorbed at surface defects such as O vacancies and step edges show little reaction under reducing conditions. We propose that regular Ti surface sites are the most active sites in photo-reactions on TiO2. PMID:26915303

Speed selection for traveling-wave solutions to the diffusion-reaction equation with cubic reaction term and Burgers nonlinear convection.

PubMed

Sabelnikov, V A; Lipatnikov, A N

2014-09-01

The problem of traveling wave (TW) speed selection for solutions to a generalized Murray-Burgers-KPP-Fisher parabolic equation with a strictly positive cubic reaction term is considered theoretically and the initial boundary value problem is numerically solved in order to support obtained analytical results. Depending on the magnitude of a parameter inherent in the reaction term (i) the term is either a concave function or a function with the inflection point and (ii) transition from pulled to pushed TW solution occurs due to interplay of two nonlinear terms; the reaction term and the Burgers convection term. Explicit pushed TW solutions are derived. It is shown that physically observable TW solutions, i.e., solutions obtained by solving the initial boundary value problem with a sufficiently steep initial condition, can be determined by seeking the TW solution characterized by the maximum decay rate at its leading edge. In the Appendix, the developed approach is applied to a non-linear diffusion-reaction equation that is widely used to model premixed turbulent combustion.

Isoprene/methyl acrylate Diels-Alder reaction in supercritical carbon dioxide

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

Lin, B.; Akgerman, A.

1999-12-01

The Diels-Alder reaction between isoprene and methyl acrylate was carried out in supercritical carbon dioxide in the temperature range 110--140 C and the pressure range 95.2--176.9 atm in a 300 cm{sup 3} autoclave. The high-pressure phase behavior of the reaction mixture in the vicinity of its critical region was determined in a mixed vessel with a sight window to ensure that all the experiments were performed in the supercritical single-phase region. Kinetic data were obtained at different temperatures, pressures, and reaction times. It was observed that in the vicinity of the critical point the reaction rate constant decreases with increasingmore » pressure. It was also determined that the reaction selectivity does not change with operating conditions. Transition-state theory was used to explain the effect of pressure on reaction rate and product selectivity. Additional experiments were conducted at constant temperature but different phase behaviors (two-phase region, liquid phase, supercritical phase) by adjusting the initial composition and pressure. It was shown that the highest reaction rate is in the supercritical region.« less

Desaturation reactions catalyzed by soluble methane monooxygenase.

PubMed

Jin, Y; Lipscomb, J D

2001-09-01

Soluble methane monooxygenase (MMO) is shown to be capable of catalyzing desaturation reactions in addition to the usual hydroxylation and epoxidation reactions. Dehydrogenated products are generated from MMO-catalyzed oxidation of certain substrates including ethylbenzene and cyclohexadienes. In the reaction of ethylbenzene, desaturation of ethyl C-H occurred along with the conventional hydroxvlations of ethyl and phenyl C-Hs. As a result, styrene is formed together with ethylphenols and phenylethanols. Similarly, when 1,3- and 1,4-cyclohexadienes were used as substrates, benzene was detected as a product in addition to the corresponding alcohols and epoxides. In all cases, reaction conditions were found to significantly affect the distribution among the different products. This new activity of MMO is postulated to be associated with the chemical properties of the substrates rather than fundamental changes in the nature of the oxygen and C-H activation chemistries. The formation of the desaturated products is rationalized by formation of a substrate cationic intermediate, possibly via a radical precursor. The cationic species is then proposed to partition between recombination (alcohol formation) and elimination (alkene production) pathways. This novel function of MMO indicates close mechanistic kinship between the hydroxylation and desaturation reactions catalyzed by the nonheme diiron clusters.

Limitations of the Weissler reaction as a model reaction for measuring the efficiency of hydrodynamic cavitation.

PubMed

Morison, K R; Hutchinson, C A

2009-01-01

The Weissler reaction in which iodide is oxidised to a tri-iodide complex (I(3)(-)) has been widely used for measurement of the intensity of ultrasonic and hydrodynamic cavitation. It was used in this work to compare ultrasonic cavitation at 24 kHz with hydrodynamic cavitation using two different devices, one a venturi and the other a sudden expansion, operated up to 8.7 bar. Hydrodynamic cavitation had a maximum efficiency of about 5 x 10(-11) moles of I(3)(-) per joule of energy compared with the maximum of almost 8 x 10(-11) mol J(-1) for ultrasonic cavitation. Hydrodynamic cavitation was found to be most effective at 10 degrees C compared with 20 degrees C and 30 degrees C and at higher upstream pressures. However, it was found that in hydrodynamic conditions, even without cavitation, I(3)(-) was consumed at a rapid rate leading to an equilibrium concentration. It was concluded that the Weissler reaction was not a good model reaction for the assessment of the effectiveness of hydrodynamic cavitation.

A statistically derived index for classifying East Coast fever reactions in cattle challenged with Theileria parva under experimental conditions.

PubMed

Rowlands, G J; Musoke, A J; Morzaria, S P; Nagda, S M; Ballingall, K T; McKeever, D J

2000-04-01

A statistically derived disease reaction index based on parasitological, clinical and haematological measurements observed in 309 5 to 8-month-old Boran cattle following laboratory challenge with Theileria parva is described. Principal component analysis was applied to 13 measures including first appearance of schizonts, first appearance of piroplasms and first occurrence of pyrexia, together with the duration and severity of these symptoms, and white blood cell count. The first principal component, which was based on approximately equal contributions of the 13 variables, provided the definition for the disease reaction index, defined on a scale of 0-10. As well as providing a more objective measure of the severity of the reaction, the continuous nature of the index score enables more powerful statistical analysis of the data compared with that which has been previously possible through clinically derived categories of non-, mild, moderate and severe reactions.

Determination of the initial exothermic reaction of shredded tyres with wire content.

PubMed

Sellasie, Kassahun G; Moo-Young, Horace K; Lloyd, Thomas

2004-10-01

This paper presents the cause of exothermic reactions in shredded tyre with exposed wire content in shredded tyre piles. Data indicate that the oxidation of exposed steel wires is the exothermic reaction in shredded tyre embankments. This would lead to spontaneous combustion. Reaction of the steel with the sulphur or the carbon black appears not to be the source of the exothermic. Laboratory tests have been conducted to determine the heat transfer properties of the materials that compose tyres (i.e., tyre rubber and wires) by using a hot-plate apparatus. In addition, one-dimensional heat conduction experiments were conducted to compare the flow of heat through the materials while varying the physical and environmental conditions. The physical conditions were the size of tyre shred, water content, and wire contents. An exothermic reaction occurred when exposed wire was present but not when it was absent. A one-dimensional heat transfer equation was developed, and parametric studies were conducted to verify the laboratory model. Exothermic reaction was found to increase linearly with temperature, size and shape of the shredded tyres, density, amount of wire in shredded tyres, and water content.

Interplay between Reaction and Phase Behaviour in Carbon Dioxide Hydrogenation to Methanol.

PubMed

Reymond, Helena; Amado-Blanco, Victor; Lauper, Andreas; Rudolf von Rohr, Philipp

2017-03-22

Condensation promotes CO 2 hydrogenation to CH 3 OH beyond equilibrium through in situ product separation. Although primordial for catalyst and reactor design, triggering conditions as well as the impact on sub-equilibrium reaction behaviour remain unclear. Herein we used an in-house designed micro-view-cell to gain chemical and physical insights into reaction and phase behaviour under high-pressure conditions over a commercial Cu/ZnO/Al 2 O 3 catalyst. Raman microscopy and video monitoring, combined with online gas chromatography analysis, allowed the complete characterisation of the reaction bulk up to 450 bar (1 bar=0.1 MPa) and 350 °C. Dew points of typical effluent streams related to a parametric study suggest that the improving reaction performance and reverting selectivities observed from 230 °C strongly correlate with (i) a regime transition from kinetic to thermodynamic, and (ii) a phase transition from a single supercritical to a biphasic reaction mixture. Our results advance a rationale behind transitioning CH 3 OH selectivities for an improved understanding of CO 2 hydrogenation under high pressure. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A laboratory test setup for in situ measurements of the dielectric properties of catalyst powder samples under reaction conditions by microwave cavity perturbation: set up and initial tests.

PubMed

Dietrich, Markus; Rauch, Dieter; Porch, Adrian; Moos, Ralf

2014-09-10

The catalytic behavior of zeolite catalysts for the ammonia-based selective catalytic reduction (SCR) of nitrogen oxides (NOX) depends strongly on the type of zeolite material. An essential precondition for SCR is a previous ammonia gas adsorption that occurs on acidic sites of the zeolite. In order to understand and develop SCR active materials, it is crucial to know the amount of sorbed ammonia under reaction conditions. To support classical temperature-programmed desorption (TPD) experiments, a correlation of the dielectric properties with the catalytic properties and the ammonia sorption under reaction conditions appears promising. In this work, a laboratory test setup, which enables direct measurements of the dielectric properties of catalytic powder samples under a defined gas atmosphere and temperature by microwave cavity perturbation, has been developed. Based on previous investigations and computational simulations, a resonator cavity and a heating system were designed, installed and characterized. The resonator cavity is designed to operate in its TM010 mode at 1.2 GHz. The first measurement of the ammonia loading of an H-ZSM-5 zeolite confirmed the operating performance of the test setup at constant temperatures of up to 300 °C. It showed how both real and imaginary parts of the relative complex permittivity are strongly correlated with the mass of stored ammonia.

On the possibility of negative activation energies in bimolecular reactions

NASA Technical Reports Server (NTRS)

Jaffe, R. L.

1978-01-01

The temperature dependence of the rate constants for model reacting systems was studied to understand some recent experimental measurements which imply the existence of negative activation energies. A collision theory model and classical trajectory calculations are used to demonstrate that the reaction probability can vary inversely with collision energy for bimolecular reactions occurring on attractive potential energy surfaces. However, this is not a sufficient condition to ensure that the rate constant has a negative temperature dependence. On the basis of these calculations, it seems unlikely that a true bimolecular reaction between neutral molecules will have a negative activation energy.

Characteristics of uranium carbonitride microparticles synthesized using different reaction conditions

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

Silva, Chinthaka M; Lindemer, Terrence; Voit, Stewart L

2014-11-01

Three sets of different experimental conditions by changing the cover gases during the sample preparation were tested to synthesize uranium carbonitride (UC1-xNx) microparticles. In the first two sets of experiments using (N2 to N2-4%H2 to Ar) and (Ar to N2 to Ar) environments, single phase UC1-xNx was synthesized. When reducing environments (Ar-4%H2 to N2-4%H2 to Ar-4%H2) were utilized, theoretical densities up to 97% of single phase UC1-xNx kernels were obtained. Physical and chemical characteristics such as density, phase purity, and chemical compositions of the synthesized UC1-xNx materials for the diferent experimental conditions used are provided. In-depth analysis of the microstruturesmore » of UC1-xNx has been carried out and is discussed with the objective of large batch fabrication of high density UC1-xNx kernels.« less

The reaction times of drivers aged 20 to 80 during a divided attention driving.

PubMed

Svetina, Matija

2016-11-16

Many studies addressing age-related changes in driving performance focus on comparing young vs. older drivers, which might lead to the biased conclusion that driving performance decreases only after the age of 65. The main aim of the study was to show that changes in driving performance are progressive throughout the adult years. A sample of 351 drivers aged 20 to 80 was assessed for their reaction times while driving between road cones. The drivers were exposed to 2 conditions varying according to task complexity. In single task conditions, the drivers performed a full stopping maneuver at a given signal; in dual task conditions, the drivers were distracted before the signal for stopping maneuver was triggered. Reaction times were compared across conditions and age groups. The results showed that both reaction times and variability of driving performance increased progressively between the ages of 20 and 80. The increase in both reaction times and variability was greater in the complex task condition. The high-performing quarter of elderly drivers performed equally well or better than younger drivers did. The data clearly supported the claim that driving performance changes steadily across age groups: both mean reaction time and interindividual variability progressively increase with age. In addition, a significant group of older drivers was identified who did not show the expected age-related decrease in performance. The findings have important implications, suggesting that in relation to driving, aging is a progressive phenomenon and may lead to variety of driving performance; age-related studies of driving performance should put more emphasis on investigating changes across the whole driver age range rather than only comparing younger and older drivers.

Synchronization criteria for generalized reaction-diffusion neural networks via periodically intermittent control.

PubMed

Gan, Qintao; Lv, Tianshi; Fu, Zhenhua

2016-04-01

In this paper, the synchronization problem for a class of generalized neural networks with time-varying delays and reaction-diffusion terms is investigated concerning Neumann boundary conditions in terms of p-norm. The proposed generalized neural networks model includes reaction-diffusion local field neural networks and reaction-diffusion static neural networks as its special cases. By establishing a new inequality, some simple and useful conditions are obtained analytically to guarantee the global exponential synchronization of the addressed neural networks under the periodically intermittent control. According to the theoretical results, the influences of diffusion coefficients, diffusion space, and control rate on synchronization are analyzed. Finally, the feasibility and effectiveness of the proposed methods are shown by simulation examples, and by choosing different diffusion coefficients, diffusion spaces, and control rates, different controlled synchronization states can be obtained.

Quantitative analysis of total starch content in wheat flour by reaction headspace gas chromatography.

PubMed

Xie, Wei-Qi; Gong, Yi-Xian; Yu, Kong-Xian

2017-09-01

This paper proposed a new reaction headspace gas chromatographic (HS-GC) method for efficiently quantifying the total starch content in wheat flours. A certain weight of wheat flour was oxidized by potassium dichromate in an acidic condition in a sealed headspace vial. The results show that the starch in wheat flour can be completely transferred to carbon dioxide at the given conditions (at 100 °C for 40 min) and the total starch content in wheat flour sample can be indirectly quantified by detecting the CO 2 formed from the oxidation reaction. The data showed that the relative standard deviation of the reaction HS-GC method in the precision test was less than 3.06%, and the relative differences between the new method and the reference method (titration method) were no more than 8.90%. The new reaction HS-GC method is automated, accurate, and can be a reliable tool for determining the total starch content in wheat flours in both laboratory and industrial applications. Graphical abstract The total starch content in wheat flour can be indirectly quantified by the GC detection of the CO 2 formed from the oxidation reaction between wheat flour and potassium dichromate in an acidic condition.

Regulation of reaction forces during the golf swing.

PubMed

McNitt-Gray, J L; Munaretto, J; Zaferiou, A; Requejo, P S; Flashner, H

2013-06-01

During the golf swing, the reaction forces applied at the feet control translation and rotation of the body-club system. In this study, we hypothesized that skilled players using a 6-iron would regulate shot distance by scaling the magnitude of the resultant horizontal reaction force applied to the each foot with minimal modifications in force direction. Skilled players (n = 12) hit golf balls using a 6-iron. Shot distance was varied by hitting the ball as they would normally and when reducing shot distance using the same club. During each swing, reaction forces were measured using dual force plates (1200 Hz) and three-dimensional kinematics were simultaneously captured (110 Hz). The results indicate that, on average, the peak resultant horizontal reaction forces of the target leg were significantly less than normal (5%, p < 0.05) when reducing shot distance. No significant differences in the orientation of the peak resultant horizontal reaction forces were observed. Resultant horizontal reaction force-angle relationships within leg and temporal relationships between target and rear legs during the swing were consistent within player across shot conditions. Regulation of force magnitude with minimal modification in force direction is expected to provide advantages from muscle activation, coordination, and performance points of view.

Method and apparatus for controlling gas evolution from chemical reactions

DOEpatents

Skorpik, James R.; Dodson, Michael G.

1999-01-01

The present invention is directed toward monitoring a thermally driven gas evolving chemical reaction with an acoustic apparatus. Signals from the acoustic apparatus are used to control a heater to prevent a run-away condition. A digestion module in combination with a robotic arm further automate physical handling of sample material reaction vessels. The invention is especially useful for carrying out sample procedures defined in EPA Methods SW-846.

Method and apparatus for controlling gas evolution from chemical reactions

DOEpatents

Skorpik, J.R.; Dodson, M.G.

1999-05-25

The present invention is directed toward monitoring a thermally driven gas evolving chemical reaction with an acoustic apparatus. Signals from the acoustic apparatus are used to control a heater to prevent a run-away condition. A digestion module in combination with a robotic arm further automate physical handling of sample material reaction vessels. The invention is especially useful for carrying out sample procedures defined in EPA Methods SW-846. 8 figs.

Kinetic and thermodynamic control in β-phenylethylamines reaction with isatin

NASA Astrophysics Data System (ADS)

Vélez, Yormari; Díaz-Oviedo, Christian; Quevedo, Rodolfo

2017-04-01

In this work it was established that dopamine's reaction with isatin produces the respective spiroisoquinoline through a Pictet-Spengler reaction whilst phenylethylamines, having less activated aromatic rings (tyramine and phenylethylamine), produce the respective imine as a mixture of stereoisomers E and Z. This article analyses the spectroscopic and structural patterns of the stereoisomers (E/Z) obtained and proposes the experimental conditions necessary for obtaining each of them as major products.

Monitoring mass transport in heterogeneously catalyzed reactions by field-gradient NMR for assessing reaction efficiency in a single pellet.

PubMed

Buljubasich, L; Blümich, B; Stapf, S

2011-09-01

An important aspect in assessing the performance of a catalytically active reactor is the accessibility of the reactive sites inside the individual pellets, and the mass transfer of reactants and products to and from these sites. Optimal design often requires a suitable combination of micro- and macropores in order to facilitate mass transport inside the pellet. In an exothermic reaction, fluid exchange between the pellet and the surrounding medium is enhanced by convection, and often by the occurrence of gas bubbles. Determining mass flow in the vicinity of a pellet thus represents a parameter for quantifying the reaction efficiency and its dependence on time or external reaction conditions. Field gradient Nuclear Magnetic Resonance (NMR) methods are suggested as a tool for providing parameters sensitive to this mass flow in a contact-free and non-invasive way. For the example of bubble-forming hydrogen peroxide decomposition in an alumina pellet, the dependence of the mean-squared displacement of fluid molecules on spatial direction, observation time and reaction time is presented, and multi-pulse techniques are employed in order to separate molecular displacements from coherent and incoherent motion on the timescale of the experiment. The reaction progress is followed until the complete decomposition of H2O2. Copyright © 2011 Elsevier Inc. All rights reserved.

Monitoring mass transport in heterogeneously catalyzed reactions by field-gradient NMR for assessing reaction efficiency in a single pellet

NASA Astrophysics Data System (ADS)

Buljubasich, L.; Blümich, B.; Stapf, S.

2011-09-01

An important aspect in assessing the performance of a catalytically active reactor is the accessibility of the reactive sites inside the individual pellets, and the mass transfer of reactants and products to and from these sites. Optimal design often requires a suitable combination of micro- and macropores in order to facilitate mass transport inside the pellet. In an exothermic reaction, fluid exchange between the pellet and the surrounding medium is enhanced by convection, and often by the occurrence of gas bubbles. Determining mass flow in the vicinity of a pellet thus represents a parameter for quantifying the reaction efficiency and its dependence on time or external reaction conditions. Field gradient Nuclear Magnetic Resonance (NMR) methods are suggested as a tool for providing parameters sensitive to this mass flow in a contact-free and non-invasive way. For the example of bubble-forming hydrogen peroxide decomposition in an alumina pellet, the dependence of the mean-squared displacement of fluid molecules on spatial direction, observation time and reaction time is presented, and multi-pulse techniques are employed in order to separate molecular displacements from coherent and incoherent motion on the timescale of the experiment. The reaction progress is followed until the complete decomposition of H 2O 2.

Effects of operational conditions on sludge degradation and organic acids formation in low-critical wet air oxidation.

PubMed

Chung, Jinwook; Lee, Mikyung; Ahn, Jaehwan; Bae, Wookeun; Lee, Yong-Woo; Shim, Hojae

2009-02-15

Wet air oxidation processes are to treat highly concentrated organic compounds including refractory materials, sludge, and night soil, and usually operated at supercritical water conditions of high temperature and pressure. In this study, the effects of operational conditions including temperature, pressure, and oxidant dose on sludge degradation and conversion into subsequent intermediates such as organic acids were investigated at low critical wet oxidation conditions. The reaction time and temperature in the wet air oxidation process was shown an important factor affecting the liquefaction of volatile solids, with more significant effect on the thermal hydrolysis reaction rather than the oxidation reaction. The degradation efficiency of sludge and the formation of organic acids were improved with longer reaction time and higher reaction temperature. For the sludge reduction and the organic acids formation under the wet air oxidation, the optimal conditions for reaction temperature, time, pressure, and oxidant dose were shown approximately 240 degrees C, 30min, 60atm, and 2.0L/min, respectively.

Ruthenium nanocatalysis on redox reactions.

PubMed

Veerakumar, Pitchaimani; Ramdass, Arumugam; Rajagopal, Seenivasan

2013-07-01

Nanoparticles have generated intense interest over the past 20 years due to their high potential applications in different areas such as catalysis, sensors, nanoscale electronics, fuel and solar cells and optoelectronics. As the large fractions of metal atoms are exposed to the surface, the use of metal nanoparticles as nanocatalysts allows mild reaction conditions and high catalytic efficiency in a large number of chemical transformations. They have emerged as sustainable heterogeneous catalysts and catalyst supports alternative to conventional materials. This review focuses on the synthesis, characterization and catalytic role of ruthenium nanoparticles (RuNPs) on the redox reactions of heteroatom containing organic compounds with the green reagent H2O2, a field that has attracted immense interest among the chemical, materials and industrial communities. We intend to present a broad overview of Ru nanocatalysts for redox reactions with an emphasis on their performance, stability and reusability. The growth in the chemistry of organic sulfoxides and N-oxides during last decade was due to their importance as synthetic intermediates for the production of a wide range of chemically and biologically active molecules. Thus design of efficient methods for the synthesis of sulfoxides and N-oxides becomes important. This review concentrates on the catalysis of RuNPs on the H2O2 oxidation of organic sulfides to sulfoxides and amines to N-oxides. The deoxygenation reactions of sulfoxides to sulfides and reduction of nitro compounds to amines are fundamental reactions in both chemistry and biology. Here, we also highlight the catalysis of metal nanoparticles on the deoxygenation of sulfoxides and sulfones and reduction of nitro compounds with particular emphasis on the mechanistic aspects.

On the implementation of a chain nuclear reaction of thermonuclear fusion on the basis of the p+11B process

NASA Astrophysics Data System (ADS)

Belyaev, V. S.; Krainov, V. P.; Zagreev, B. V.; Matafonov, A. P.

2015-07-01

Various theoretical and experimental schemes for implementing a thermonuclear reactor on the basis of the p+11B reaction are considered. They include beam collisions, fusion in degenerate plasmas, ignition upon plasma acceleration by ponderomotive forces, and the irradiation of a solid-state target from 11B with a proton beam under conditions of a Coulomb explosion of hydrogen microdrops. The possibility of employing ultra-short high-intensity laser pulses to initiate the p+11B reaction under conditions far from thermodynamic equilibrium is discussed. This and some other weakly radioactive thermonuclear reactions are promising owing to their ecological cleanness—there are virtually no neutrons among fusion products. Nuclear reactions that follow the p+11B reaction may generate high-energy protons, sustaining a chain reaction, and this is an advantage of the p+11B option. The approach used also makes it possible to study nuclear reactions under conditions close to those in the early Universe or in the interior of stars.

Investigation of the relationship between CO2 reservoir rock property change and the surface roughness change originating from the supercritical CO2-sandstone-groundwater geochemical reaction at CO2 sequestration condition

NASA Astrophysics Data System (ADS)

Lee, Minhee; Wang, Sookyun; Kim, Seyoon; Park, Jinyoung

2015-04-01

Lab scale experiments were performed to investigate the property changes of sandstone slabs and cores, resulting from the scCO2-rock-groundwater reaction for 180 days under CO2 sequestration conditions (100 bar and 50 °C). The geochemical reactions, including the surface roughness change of minerals in the slab, resulted from the dissolution and the secondary mineral precipitation for the sandstone reservoir of the Gyeongsang basin, Korea were reproduced in laboratory scale experiments and the relationship between the geochemical reaction and the physical rock property change was derived, for the consideration of successful subsurface CO2 sequestration. The use of the surface roughness value (SRrms) change rate and the physical property change rate to quantify scCO2-rock-groundwater reaction is the novel approach on the study area for CO2 sequestration in the subsurface. From the results of SPM (Scanning Probe Microscope) analyses, the SRrms for each sandstone slab was calculated at different reaction time. The average SRrms increased more than 3.5 times during early 90 days reaction and it continued to be steady after 90 days, suggesting that the surface weathering process of sandstone occurred in the early reaction time after CO2 injection into the subsurface reservoir. The average porosity of sandstone cores increased by 8.8 % and the average density decreased by 0.5 % during 90 days reaction and these values slightly changed after 90 days. The average P and S wave velocities of sandstone cores also decreased by 10 % during 90 days reaction. The trend of physical rock property change during the geochemical reaction showed in a logarithmic manner and it was also correlated to the logarithmic increase in SRrms, suggesting that the physical property change of reservoir rocks originated from scCO2 injection directly comes from the geochemical reaction process. Results suggested that the long-term estimation of the physical property change for reservoir rocks in CO2

The Kinetic Behavior of Benzaldehyde under Hydrothermal Conditions

NASA Astrophysics Data System (ADS)

Fecteau, K.; Gould, I.; Hartnett, H. E.; Williams, L. B.; Shock, E.

2013-12-01

Aldehydes represent an intermediate redox state between alcohols and carboxylic acids and are likely intermediates in the transformation of organic compounds in natural systems. We have conducted kinetic studies of a model aldehyde, benzaldehyde, in high-temperature water (250-350 °C, saturation pressure) in clear fused quartz (CFQ) autoclaves. Under these conditions, benzaldehyde is observed to undergo a disproportionation reaction to benzyl alcohol and benzoic acid reminiscent of the base-catalyzed Cannizzaro reaction known to occur at cooler temperatures. Benzene is also produced via decarbonylation of the aldehyde. We have obtained pseudo second-order rate constants for the decomposition of benzaldehyde at 250, 300, and 350 °C. Rates derived via repeated heating phases and subsequent quantitative 13C-NMR spectroscopy of a single NMR-compatible CFQ tube containing isotopically labeled benzaldehyde are consistent with those obtained by analysis of product suites from individual timed experiments via gas chromatography. Arrhenius parameters for these rate constants are consistent with published values for the reaction under supercritical conditions from one study (Tsao et al. 1992) yet the pre-exponential factor is approximately 7 orders of magnitude smaller than that derived from another study (Ikushima et al. 2001). Moreover, fitting our rate constants with the Eyring equation yields an entropy of activation (ΔS‡) of -26.6 kcal mol-1 K-1, which is consistent for a bimolecular transition state at the rate-limiting step. In contrast, the rates of Ikushima et al. yield a positive value of ΔS‡, which is inconsistent with the putative mechanism for the reaction. The linear Arrhenius behavior of the decomposition of benzaldehyde from high-temperature liquid to supercritical conditions demonstrates the potential for extrapolating experimentally derived rates of reactions for organic functional group transformations to conditions where diagenesis, alteration

Applications of Palladium-Catalyzed C-N Cross-Coupling Reactions.

PubMed

Ruiz-Castillo, Paula; Buchwald, Stephen L

2016-10-12

Pd-catalyzed cross-coupling reactions that form C-N bonds have become useful methods to synthesize anilines and aniline derivatives, an important class of compounds throughout chemical research. A key factor in the widespread adoption of these methods has been the continued development of reliable and versatile catalysts that function under operationally simple, user-friendly conditions. This review provides an overview of Pd-catalyzed N-arylation reactions found in both basic and applied chemical research from 2008 to the present. Selected examples of C-N cross-coupling reactions between nine classes of nitrogen-based coupling partners and (pseudo)aryl halides are described for the synthesis of heterocycles, medicinally relevant compounds, natural products, organic materials, and catalysts.

Applications of Palladium-Catalyzed C–N Cross-Coupling Reactions

PubMed Central

2016-01-01

Pd-catalyzed cross-coupling reactions that form C–N bonds have become useful methods to synthesize anilines and aniline derivatives, an important class of compounds throughout chemical research. A key factor in the widespread adoption of these methods has been the continued development of reliable and versatile catalysts that function under operationally simple, user-friendly conditions. This review provides an overview of Pd-catalyzed N-arylation reactions found in both basic and applied chemical research from 2008 to the present. Selected examples of C–N cross-coupling reactions between nine classes of nitrogen-based coupling partners and (pseudo)aryl halides are described for the synthesis of heterocycles, medicinally relevant compounds, natural products, organic materials, and catalysts. PMID:27689804

Reaction mechanism for the aqueous-phase mineral carbonation of heat-activated serpentine at low temperatures and pressures in flue gas conditions.

PubMed

Pasquier, Louis-César; Mercier, Guy; Blais, Jean-François; Cecchi, Emmanuelle; Kentish, Sandra

2014-05-06

Mineral carbonation is known as one of the safest ways to sequester CO2. Nevertheless, the slow kinetics and low carbonation rates constitute a major barrier for any possible industrial application. To date, no studies have focused on reacting serpentinite with a relatively low partial pressure of CO2 (pCO2) close to flue gas conditions. In this work, finely ground and heat-treated serpentinite [Mg3Si2O5(OH)4] extracted from mining residues was reacted with a 18.2 vol % CO2 gas stream at moderate global pressures to investigate the effect on CO2 solubility and Mg leaching. Serpentinite dissolution rates were also measured to define the rate-limiting step. Successive batches of gas were contacted with the same serpentinite to identify surface-limiting factors using scanning electron microscopy (SEM) analysis. Investigation of the serpentinite carbonation reaction mechanisms under conditions close to a direct flue gas treatment showed that increased dissolution rates could be achieved relative to prior work, with an average Mg dissolution rate of 3.55 × 10(-11) mol cm(-2) s(-1). This study provides another perspective of the feasibility of applying a mineral carbonation process to reduce industrial greenhouse gas (GHG) emissions from large emission sources.

Fe(II)/Fe(III)-Catalyzed Intramolecular Didehydro-Diels-Alder Reaction of Styrene-ynes.

PubMed

Mun, Hyeon Jin; Seong, Eun Young; Ahn, Kwang-Hyun; Kang, Eun Joo

2018-02-02

The intramolecular didehydro-Diels-Alder reaction of styrene-ynes was catalyzed by Fe(II) and Fe(III) to produce various naphthalene derivatives under microwave heating conditions. Mechanistic calculations found that the Fe(II) catalyst activates the styrenyl diene in an inverse-electron-demand Diels-Alder reaction, and the consecutive dehydrogenation reaction can be promoted by either Fe(II)-catalyzed direct dehydrogenation or an Fe(III)-catalyzed rearomatization/dehydrogenation pathway.

Overwork accelerates thrombotic reaction: implications for the pathogenesis of Karoshi.

PubMed

Otsui, Kazunori; Yamamoto, Junichiro; Inoue, Nobutaka

2018-02-01

Work-related stressors are potential causes of cardiovascular diseases (CVDs) and stroke; however, the pathophysiological mechanisms by which occupational stress induces and exacerbates CVDs remain unclear. The global thrombosis test (GTT) is a novel in vitro assay for evaluating both thrombotic reactions and subsequent thrombolysis. The time required to form an occlusive thrombus with the GTT, called as the occlusion time (OT), and the time to lyse the thrombus, the lysis time (LT), are markers of thrombotic and thrombolytic reactions, respectively. We investigated the impact of work-related stress on the thrombotic and thrombolytic reactions in 46 healthy medical residents. Off-duty or on-duty blood samples were collected on the mornings of non-work days or after the night duty on the emergent room respectively. The duration of sleep was significantly shorter during night duty than during off-duty nights [2.25 (1.0, 3.0) h vs. 6.0 (5.0, 7.0) h; p < 0.001]. Baseline OT was 310.3 (260.9, 437.7) s. whereas the on-duty OT was significantly shortened [284.2 (230.5, 355.8) s; p < 0.01]. LT was significantly prolonged during overwork conditions compared with off-duty conditions [1547 (1346, 1908) s vs. 1470 (1219, 1692) s; p < 0.05]. Overwork accelerates the thrombotic reactions. These reactions might explain the pathogenesis of overwork-related CVDs. The GTT is a good tool for evaluating of the level of fatigue.

The synthesis of highly functionalised pyridines using Ghosez-type reactions of dihydropyrazoles.

PubMed

Catti, Federica; Kiuru, Paula S; Slawin, Alexandra M Z; Westwood, Nicholas J

2008-09-29

The aza-Diels-Alder reaction of αβ-unsaturated hydrazones is a general methodology that has been applied both to the synthesis of natural products and in the development of multicomponent reactions. Trends have emerged as to the effect of substituents on the efficiency of this reaction with substituents at the C2 and C4-positions of the aza-diene in general suppressing the reaction. Here we report that 4,5-dihydropyrazoles can function as substrates in this process despite the presence of substituents at both of these positions. A one pot, four chemical step sequence carried out under standard thermal or microwave conditions results in the formation of the corresponding pyridine-containing compounds. The scope of the reaction is explored and additional insights into the proposed mechanism of this reaction are provided.

Hydroamination reactions of alkynes with ortho-substituted anilines in ball mills: synthesis of benzannulated N-heterocycles by a cascade reaction.

PubMed

Weiße, Maik; Zille, Markus; Jacob, Katharina; Schmidt, Robert; Stolle, Achim

2015-04-20

It was demonstrated that ortho-substituted anilines are prone to undergo hydroamination reactions with diethyl acetylenedicarboxylate in a planetary ball mill. A sequential coupling of the intermolecular hydroamination reaction with intramolecular ring closure was utilized for the syntheses of benzooxazines, quinoxalines, and benzothiazines from readily available building blocks, that is, electrophilic alkynes and anilines with OH, NH, or SH groups in the ortho position. For the heterocycle formation, it was shown that several stress conditions were able to initiate the reaction in the solid state. Processing in a ball mill seemed to be advantageous over comminution with mortar and pestle with respect to process control. In the latter case, significant postreaction modification occurred during solid-state analysis. Cryogenic milling proved to have an adverse effect on the molecular transformation of the reagents. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lipid synthesis under hydrothermal conditions by Fischer-Tropsch-type reactions

NASA Technical Reports Server (NTRS)

McCollom, T. M.; Ritter, G.; Simoneit, B. R.

1999-01-01

Ever since their discovery in the late 1970's, mid-ocean-ridge hydrothermal systems have received a great deal of attention as a possible site for the origin of life on Earth (and environments analogous to mid-ocean-ridge hydrothermal systems are postulated to have been sites where life could have originated or Mars and elsewhere as well). Because no modern-day terrestrial hydrothermal systems are free from the influence of organic compounds derived from biologic processes, laboratory experiments provide the best opportunity for confirmation of the potential for organic synthesis in hydrothermal systems. Here we report on the formation of lipid compounds during Fischer-Tropsch-type synthesis from aqueous solutions of formic acid or oxalic acid. Optimum synthesis occurs in stainless steel vessels by heating at 175 degrees C for 2-3 days and produces lipid compounds ranging from C2 to > C35 which consist of n-alkanols, n-alkanoic acids, n-alkenes, n-alkanes and alkanones. The precursor carbon sources used are either formic acid or oxalic acid, which disproportionate to H2, CO2 and probably CO. Both carbon sources yield the same lipid classes with essentially the same ranges of compounds. The synthesis reactions were confirmed by using 13C labeled precursor acids.

Lipid Synthesis Under Hydrothermal Conditions by Fischer- Tropsch-Type Reactions

NASA Astrophysics Data System (ADS)

McCollom, Thomas M.; Ritter, Gilles; Simoneit, Bernd R. T.

1999-03-01

Ever since their discovery in the late 1970's, mid-ocean-ridge hydrothermal systems have received a great deal of attention as a possible site for the origin of life on Earth (and environments analogous to mid-ocean-ridge hydrothermal systems are postulated to have been sites where life could have originated on Mars and elsewhere as well). Because no modern-day terrestrial hydrothermal systems are free from the influence of organic compounds derived from biologic processes, laboratory experiments provide the best opportunity for confirmation of the potential for organic synthesis in hydrothermal systems. Here we report on the formation of lipid compounds during Fischer-Tropsch-type synthesis from aqueous solutions of formic acid or oxalic acid. Optimum synthesis occurs in stainless steel vessels by heating at 175 °C for 2-3 days and produces lipid compounds ranging from C2 to >C35 which consist of n-alkanols, n- alkanoic acids, n-alkenes, n-alkanes and alkanones. The precursor carbon sources used are either formic acid or oxalic acid, which disproportionate to H2, CO2 and probably CO. Both carbon sources yield the same lipid classes with essentially the same ranges of compounds. The synthesis reactions were confirmed by using 13C labeled precursor acids.

Lipid synthesis under hydrothermal conditions by Fischer-Tropsch-type reactions.

PubMed

McCollom, T M; Ritter, G; Simoneit, B R

1999-03-01

Ever since their discovery in the late 1970's, mid-ocean-ridge hydrothermal systems have received a great deal of attention as a possible site for the origin of life on Earth (and environments analogous to mid-ocean-ridge hydrothermal systems are postulated to have been sites where life could have originated or Mars and elsewhere as well). Because no modern-day terrestrial hydrothermal systems are free from the influence of organic compounds derived from biologic processes, laboratory experiments provide the best opportunity for confirmation of the potential for organic synthesis in hydrothermal systems. Here we report on the formation of lipid compounds during Fischer-Tropsch-type synthesis from aqueous solutions of formic acid or oxalic acid. Optimum synthesis occurs in stainless steel vessels by heating at 175 degrees C for 2-3 days and produces lipid compounds ranging from C2 to > C35 which consist of n-alkanols, n-alkanoic acids, n-alkenes, n-alkanes and alkanones. The precursor carbon sources used are either formic acid or oxalic acid, which disproportionate to H2, CO2 and probably CO. Both carbon sources yield the same lipid classes with essentially the same ranges of compounds. The synthesis reactions were confirmed by using 13C labeled precursor acids.

Reaction Decoder Tool (RDT): extracting features from chemical reactions.

PubMed

Rahman, Syed Asad; Torrance, Gilliean; Baldacci, Lorenzo; Martínez Cuesta, Sergio; Fenninger, Franz; Gopal, Nimish; Choudhary, Saket; May, John W; Holliday, Gemma L; Steinbeck, Christoph; Thornton, Janet M

2016-07-01

Extracting chemical features like Atom-Atom Mapping (AAM), Bond Changes (BCs) and Reaction Centres from biochemical reactions helps us understand the chemical composition of enzymatic reactions. Reaction Decoder is a robust command line tool, which performs this task with high accuracy. It supports standard chemical input/output exchange formats i.e. RXN/SMILES, computes AAM, highlights BCs and creates images of the mapped reaction. This aids in the analysis of metabolic pathways and the ability to perform comparative studies of chemical reactions based on these features. This software is implemented in Java, supported on Windows, Linux and Mac OSX, and freely available at https://github.com/asad/ReactionDecoder : asad@ebi.ac.uk or s9asad@gmail.com. © The Author 2016. Published by Oxford University Press.

The Reaction Titanite+Kyanite=Anorthite+Rutile and Titanite-Rutile Barometry in Eclogites

USGS Publications Warehouse

Manning, C.F.; Bohlen, S.R.

1991-01-01

Titanite and rutile are a common mineral pair in eclogites, and many equilibria involving these phases are potentially useful in estimating pressures of metamorphism. We have reversed one such reaction, {Mathematical expression} using a piston-cylinder apparatus. Titanite+kyanite is the high-pressure assemblage and our results locate the equilibrium between 15.5 15.9, 17.7-17.9, 18.8-19.0, and 20.0-20.2 kb at 900, 1000, 1050, and 1100??C, respectively. The experiments require a positive dP/dT of between 20.5 and 23.5 bars/??C for the reaction. We use the reversed equilibrium and two other reactions, {Mathematical expression} and {Mathematical expression} to calculate metamorphic conditions for three eclogite localities. Using these reactions in conjunction with garnet-clinopyroxene Fe2+-Mg exchange equilibria, conditions of metamorphism were 16 kb and 750??C for kyaniteeclogites from Glenelg, Scotland, 21 kb and 625??C for eclogite-facies mica schists from the Tauern Window, Austria, and 46 kb and 850??C for eclogite-facies biotite gneisses from the Kokchetav Massif, USSR. For the Scottish and Austrian eclogites, the pressures derived from the titanite-rutile reactions provide additional constraints on pressures for these localities, leading to precise estimates of metamorphic conditions. In the case of the Soviet Union eclogites, the results show that the silicate-oxide assemblage is consistent with the remarkable occurrence of diamond inclusions in the garnets. The results of this study suggest that titanite and rutile stably coexist in many eclogites and that titanite solid solutions are ideal or nearly so. ?? 1991 Springer-Verlag.

Photocatalytic fluoroalkylation reactions of organic compounds.

PubMed

Barata-Vallejo, Sebastián; Bonesi, Sergio M; Postigo, Al

2015-12-14

Photocatalytic methods for fluoroalkyl-radical generation provide more convenient alternatives to the classical perfluoroalkyl-radical (Rf) production through chemical initiators, such as azo or peroxide compounds or the employment of transition metals through a thermal electron transfer (ET) initiation process. The mild photocatalytic reaction conditions tolerate a variety of functional groups and, thus, are handy to the late-stage modification of bioactive molecules. Transition metal-photocatalytic reactions for Rf radical generation profit from the redox properties of coordinatively saturated Ru or Ir organocomplexes to act as both electron donor and reductive species, thus allowing for the utilization of electron accepting and donating fluoroalkylating agents for Rf radical production. On the other hand, laboratory-available and inexpensive photoorgano catalysts (POC), in the absence of transition metals, can also act as electron exchange species upon excitation, resulting in ET reactions that produce Rf radicals. In this work, a critical account of transition metal and transition metal-free Rf radical production will be described with photoorgano catalysts, studying classical examples and the most recent investigations in the field.

Chemical reaction networks as a model to describe UVC- and radiolytically-induced reactions of simple compounds.

PubMed

Dondi, Daniele; Merli, Daniele; Albini, Angelo; Zeffiro, Alberto; Serpone, Nick

2012-05-01

When a chemical system is submitted to high energy sources (UV, ionizing radiation, plasma sparks, etc.), as is expected to be the case of prebiotic chemistry studies, a plethora of reactive intermediates could form. If oxygen is present in excess, carbon dioxide and water are the major products. More interesting is the case of reducing conditions where synthetic pathways are also possible. This article examines the theoretical modeling of such systems with random-generated chemical networks. Four types of random-generated chemical networks were considered that originated from a combination of two connection topologies (viz., Poisson and scale-free) with reversible and irreversible chemical reactions. The results were analyzed taking into account the number of the most abundant products required for reaching 50% of the total number of moles of compounds at equilibrium, as this may be related to an actual problem of complex mixture analysis. The model accounts for multi-component reaction systems with no a priori knowledge of reacting species and the intermediates involved if system components are sufficiently interconnected. The approach taken is relevant to an earlier study on reactions that may have occurred in prebiotic systems where only a few compounds were detected. A validation of the model was attained on the basis of results of UVC and radiolytic reactions of prebiotic mixtures of low molecular weight compounds likely present on the primeval Earth.

Chemical Reaction Engineering: Current Status and Future Directions.

ERIC Educational Resources Information Center

Dudukovic, M. P.

1987-01-01

Describes Chemical Reaction Engineering (CRE) as the discipline that quantifies the interplay of transport phenomena and kinetics in relating reactor performance to operating conditions and input variables. Addresses the current status of CRE in both academic and industrial settings and outlines future trends. (TW)

Temperature dependence of carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals under atmospherically relevant conditions

NASA Astrophysics Data System (ADS)

Piansawan, Tammarat; Saccon, Marina; Laumer, Werner; Gensch, Iulia; Kiendler-Scharr, Astrid

2015-04-01

Modeling of the global distribution of atmospheric ethane sources and sinks by using the 13C isotopic composition requires accurate knowledge of the carbon kinetic isotope effect (KIE) of its atmospheric removal reactions. The quantum mechanical prediction implies the necessity to elucidate the temperature dependence of KIE within atmospherically relevant temperature range by experiment. In this study, the KIE and its temperature dependence for ethane oxidation by OH radicals was investigated at ambient pressure in a temperature range of 243 K to 303 K. The chemical reactions were carried out in a 15 L PFE reaction chamber, suspended in a thermally controlled oven. The isotope ratios of the gas phase components during the course of the reactions were measured by Thermal Desorption -- Gas Chromatography -- Isotope Ratio Mass Spectrometry (TD-GC-IRMS). For each temperature, the KIE was derived from the temporal evolution of the concentration and stable carbon isotope ratio (δ13C) of ethane using a method adapted from the relative reaction rate concept. The room temperature KIE of the ethane reaction with OH radicals was found to be 6.85 ± 0.32 ‰. This value is in agreement with the previously reported value of 8.57 ± 1.95 ‰ [Anderson et al. 2004] but has a substantially lower uncertainty. The experimental results will be discussed with the KIE temperature dependence predicted by quantum mechanical calculations. Reference: Rebecca S. Anderson, Lin Huang, Richard Iannone, Alexandra E. Thompson, and Jochen Rudolph (2004), Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K, J. Phys. Chem. A, 108, 11537--11544

Chlorination of tramadol: Reaction kinetics, mechanism and genotoxicity evaluation.

PubMed

Cheng, Hanyang; Song, Dean; Chang, Yangyang; Liu, Huijuan; Qu, Jiuhui

2015-12-01

Tramadol (TRA) is one of the most detected analgesics in environmental matrices, and it is of high significance to study the reactivity of TRA during chlorination considering its potential toxicity to the environment. The chlorine/TRA reaction is first order with respect to the TRA concentration, and a combination of first-order and second-order with respect to chlorine concentration. The pH dependence of the observed rate constants (kobs) showed that the TRA oxidation reactivity increased with increasing pH. kobs can be quantitatively described by considering all active species including Cl2, Cl2O and HOCl, and the individual rate constants of HOCl/TRA(0), HOCl/TRAH(+), Cl2/TRA and Cl2O/TRA reactions were calculated to be (2.61±0.29)×10(3)M(-1)s(-1), 14.73±4.17M(-1)s(-1), (3.93±0.34)×10(5)M(-1)s(-1) and (5.66±1.83)×10(6)M(-1)s(-1), respectively. Eleven degradation products were detected with UPLC-Q-TOF-MS, and the corresponding structures of eight products found under various pH conditions were proposed. The amine group was proposed to be the initial attack site under alkaline pH conditions, where reaction of the deprotonated amine group with HOCl is favorable. Under acidic and neutral pH conditions, however, two possible reaction pathways were proposed. One is an electrophilic substitution on the aromatic ring, and another is an electrophilic substitution on the nitrogen, leading to an N-chlorinated intermediate, which can be further oxidized. Finally, the SOS/umu test showed that the genotoxicity of TRA chlorination products increased with increasing dosage of chlorine, which was mostly attributed to the formation of some chlorine substitution products. Copyright © 2015 Elsevier Ltd. All rights reserved.

The effect of reaction conditions on formation of wet precipitated calcium phosphates

NASA Astrophysics Data System (ADS)

Huang, Chen; Cao, Peng

2015-03-01

The precipitation process discussed in the present study involves the addition of alkaline solutions to an acidic calcium phosphate suspension. Several parameters (pH, pH buffer reagent, ageing and stirring) were investigated. The synthesized powders were calcined at 1000°C for 1 h in air, in order to study the thermal stability and crystalline phase compositions. X-ray diffraction (XRD) and ESEM analysis were used for sample characterization. It is found that all these processing parameters affect the crystalline phases evolved and resultant microstructures. Phase evolution occurred at an elevated pH level. The pH buffer reagent would affect both the phase composition and microstructure. Ageing was essential for the phase maturation. Stirring accelerated the reaction process by providing a homogeneous medium for precipitation.

Method of introducing additive into a reaction gas flow

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

Michelfelder, S.; Chughtai, M.Y.

1984-04-03

A method of continuously introducing additive, which is conveyed by gaseous and/or liquid carriers, into a turbulent reaction gas flow in the combustion chamber of a steam generator having dry ash withdrawal for selective removal, in a dry manner, of environmentally harmful gaseous noxious materials, such as sulfur, chlorine, and chlorine compounds, which are contained in a hot reaction gas flow which results after a complete or incomplete flame combustion of solid, liquid, or gaseous fuels. Depending upon the additive introduced, heat is stored and/or used for decomposition reactions. The additive, is first introduced at one or more input locations,more » due to locally different pressure conditions in the combustion chamber, into one or more recirculation flows which are within the system and are closed. The additive is subsequently withdrawn from these recirculation flows and is introduced into the reaction gas flow.« less

Gasification Reaction Characteristics of Ferro-Coke at Elevated Temperatures

NASA Astrophysics Data System (ADS)

Wang, Peng; Zhang, Jian-liang; Gao, Bing

2017-01-01

In this paper, the effects of temperature and atmosphere on the gasification reaction of ferro-coke were investigated in consideration of the actual blast furnace conditions. Besides, the microstructure of the cokes was observed by scanning electron microscope (SEM). It is found that the weight loss of ferro-coke during the gasification reaction is significantly enhanced in the case of increasing either the reaction temperature or the CO2 concentration. Furthermore, compared with the normal type of metallurgical coke, ferro-coke exhibits a higher weight loss when they are gasified at the same temperature or under the same atmosphere. As to the microstructure, inside the reacted ferro-coke are a large amount of pores. Contrary to the normal coke, the proportions of the large-size pores and the through holes are greatly increased after gasification, giving rise to thinner pore walls and hence a degradation in coke strength after reaction (CSR).

Chemical reactions at aqueous interfaces

NASA Astrophysics Data System (ADS)

Vecitis, Chad David

2009-12-01

Interfaces or phase boundaries are a unique chemical environment relative to individual gas, liquid, or solid phases. Interfacial reaction mechanisms and kinetics are often at variance with homogeneous chemistry due to mass transfer, molecular orientation, and catalytic effects. Aqueous interfaces are a common subject of environmental science and engineering research, and three environmentally relevant aqueous interfaces are investigated in this thesis: 1) fluorochemical sonochemistry (bubble-water), 2) aqueous aerosol ozonation (gas-water droplet), and 3) electrolytic hydrogen production and simultaneous organic oxidation (water-metal/semiconductor). Direct interfacial analysis under environmentally relevant conditions is difficult, since most surface-specific techniques require relatively `extreme' conditions. Thus, the experimental investigations here focus on the development of chemical reactors and analytical techniques for the completion of time/concentration-dependent measurements of reactants and their products. Kinetic modeling, estimations, and/or correlations were used to extract information on interfacially relevant processes. We found that interfacial chemistry was determined to be the rate-limiting step to a subsequent series of relatively fast homogeneous reactions, for example: 1) Pyrolytic cleavage of the ionic headgroup of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) adsorbed to cavitating bubble-water interfaces during sonolysis was the rate-determining step in transformation to their inorganic constituents carbon monoxide, carbon dioxide, and fluoride; 2) ozone oxidation of aqueous iodide to hypoiodous acid at the aerosol-gas interface is the rate-determining step in the oxidation of bromide and chloride to dihalogens; 3) Electrolytic oxidation of anodic titanol surface groups is rate-limiting for the overall oxidation of organics by the dichloride radical. We also found chemistry unique to the interface, for example: 1

Assessment of PDF Micromixing Models Using DNS Data for a Two-Step Reaction

NASA Astrophysics Data System (ADS)

Tsai, Kuochen; Chakrabarti, Mitali; Fox, Rodney O.; Hill, James C.

1996-11-01

Although the probability density function (PDF) method is known to treat the chemical reaction terms exactly, its application to turbulent reacting flows have been overshadowed by the ability to model the molecular mixing terms satisfactorily. In this study, two PDF molecular mixing models, the linear-mean-square-estimation (LMSE or IEM) model and the generalized interaction-by-exchange-with-the-mean (GIEM) model, are compared with the DNS data in decaying turbulence with a two-step parallel-consecutive reaction and two segregated initial conditions: ``slabs" and ``blobs". Since the molecular mixing model is expected to have a strong effect on the mean values of chemical species under such initial conditions, the model evaluation is intended to answer the following questions: Can the PDF models predict the mean values of chemical species correctly with completely segregated initial conditions? (2) Is a single molecular mixing timescale sufficient for the PDF models to predict the mean values with different initial conditions? (3) Will the chemical reactions change the molecular mixing timescales of the reacting species enough to affect the accuracy of the model's prediction for the mean values of chemical species?

Quasiglobal reaction model for ethylene combustion

NASA Technical Reports Server (NTRS)

Singh, D. J.; Jachimowski, Casimir J.

1994-01-01

The objective of this study is to develop a reduced mechanism for ethylene oxidation. The authors are interested in a model with a minimum number of species and reactions that still models the chemistry with reasonable accuracy for the expected combustor conditions. The model will be validated by comparing the results to those calculated with a detailed kinetic model that has been validated against the experimental data.

An investigation into the reactions of biochar in soil

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

Joseph, Stephen; Camps-Arbestain, Marta; Lin, Yun

2010-10-12

Interactions between biochar, soil, microbes and plant roots may occur within a short period of time after application to the soil. The extent, rates and implications of these interactions, however, are far from being understood. This review includes a description of the properties of biochars and suggests possible reactions that may occur after the addition of biochars to soil. These include dissolution-precipitation, adsorption-desorption, acid-base and redox reactions. Special attention is given to reactions occurring within pores, and to interactions with roots, microorganisms and soil fauna. The examination of biochars (from chicken litter, greenwaste and paper mill sludges) weathered for onemore » and two years in an Australian Ferrosol provides evidence for some of the mechanisms described in this review and offers an insight to reactions at a molecular scale. These interactions are biochar- and site-specific. Therefore, suitable experimental trials combining biochar types and different pedoclimatic conditions are needed to determine the extent to which these reactions influence the potential of biochar as a soil amendment and C-sequestration tool.« less

14 CFR Appendix C to Part 23 - Basic Landing Conditions

Code of Federal Regulations, 2011 CFR

2011-01-01

... 14 Aeronautics and Space 1 2011-01-01 2011-01-01 false Basic Landing Conditions C Appendix C to... to Part 23—Basic Landing Conditions [C23.1 Basic landing conditions] Condition Tail wheel type Level landing Tail-down landing Nose wheel type Level landing with inclined reactions Level landing with nose...

Cross-reactions between xanthates and rubber additives.

PubMed

Sasseville, Denis; Al-Sowaidi, Mowza; Moreau, Linda

2007-09-01

We previously described allergic contact dermatitis from xanthates used in the recovery of metals from mining ores. We observed cross-reactions with carbamates, believed to be due to the common "dithio" nucleus shared by both groups. The present study was undertaken to establish the rate of cross-reactions between xanthates and rubber additives. Between November 2002 and December 2005, 1,220 consecutive patients were patch-tested with sodium isopropyl xanthate 10% in petrolatum (pet) and with potassium amyl xanthate 10% pet and later 5% pet, in addition to the North American Contact Dermatitis Group standard series and other series as required by their conditions. Fifty-one patients reacted to xanthates, carbamates, or thiurams; 26 reacted to xanthates only, and these reactions were felt to be irritant. Twenty-five patients reacted to xanthates and/or to one or more of the rubber additives, 12 had positive reactions to xanthates and to either carba mix or thiuram mix, 10 reacted to xanthates and carba mix, 9 reacted to xanthates and thiuram mix, and 8 showed positive reactions to xanthates and both mixes. However, 13 patients had positive reactions to carba mix and thiuram mix but did not react to xanthates. Six patients reacted to other rubber additives such as mercaptobenzothiazole, black rubber mix, and mixed dialkyl thioureas. Five of these patients also reacted to xanthates, 4 reacted to xanthates and carba mix, and 3 reacted to xanthates, carba mix, and thiuram mix. Of patients sensitized to carbamates, thiurams, or mercaptobenzothiazole, 50% exhibit cross-reactions with xanthates. Xanthates are irritants, and their patch-test concentrations should be lowered to 5% or less.

Chemical and thermal stability of N-heterocyclic ionic liquids in catalytic C-H activation reactions.

PubMed

Chen, Guanyi; Kang, Shujuan; Ma, Qisheng; Chen, Weiqun; Tang, Yongchun

2014-11-01

(1)H-NMR spectrum analyses are applied to study the chemical and thermal stability of selected N-heterocyclic ionic liquids within the reaction system that can highly efficiently activate a C-H bond of methane and convert it into the C-O bond in methanol. Our results indicate that under such reaction conditions involving using a powerful Pt-based catalyst and strong acidic solvent, the aromatic ring of an imidazolium cation becomes unstable generating an ammonium ion (NH(4)(+)). Our results also suggest that the instability of the imidazolium ring is more chemically (participation in reactions) than thermally based. Modifications of the aromatic ring structure such as pyrazolium and triazolium cations can increase the chemical/thermal stability of ionic liquids under these reaction conditions. Copyright © 2014 John Wiley & Sons, Ltd.

Revisiting and Computing Reaction Coordinates with Directional Milestoning

PubMed Central

Kirmizialtin, Serdal; Elber, Ron

2011-01-01

The method of Directional Milestoning is revisited. We start from an exact and more general expression and state the conditions and validity of the memory-loss approximation. An algorithm to compute a reaction coordinate from Directional Milestoning data is presented. The reaction coordinate is calculated as a set of discrete jumps between Milestones that maximizes the flux between two stable states. As an application we consider a conformational transition in solvated Adenosine. We compare a long molecular dynamic trajectory with Directional Milestoning and discuss the differences between the maximum flux path and minimum energy coordinates. PMID:21500798

A new necessary condition for Turing instabilities.

PubMed

Elragig, Aiman; Townley, Stuart

2012-09-01

Reactivity (a.k.a initial growth) is necessary for diffusion driven instability (Turing instability). Using a notion of common Lyapunov function we show that this necessary condition is a special case of a more powerful (i.e. tighter) necessary condition. Specifically, we show that if the linearised reaction matrix and the diffusion matrix share a common Lyapunov function, then Turing instability is not possible. The existence of common Lyapunov functions is readily checked using semi-definite programming. We apply this result to the Gierer-Meinhardt system modelling regenerative properties of Hydra, the Oregonator, to a host-parasite-hyperparasite system with diffusion and to a reaction-diffusion-chemotaxis model for a multi-species host-parasitoid community. Copyright © 2012 Elsevier Inc. All rights reserved.

Catalytical Conversion of Carbohydrates into Lactic Acid via Hydrothermal Reaction

NASA Astrophysics Data System (ADS)

Wei, Zhen; Jin, Fangming; Zhang, Guangyi; Zhang, Shiping; Yao, Guodong

2010-11-01

This paper focuses on catalytical conversion of carbohydrates into lactic acid, under the hydrothermal conditions, which may have a promising future for its high speediness and effectiveness. The catalysis of ZnO was investigated to improve the lactic acid yields. The results showed that the lactic acid yields increased immensely by the addition of ZnO. The effects of the reaction time and the addition amount of ZnO on the conversion of carbohydrates to lactic acid were studied. The highest lactic acid yields reached up to 28% starting from glucose after the reaction time of 60 s under the conditions of 0.2 mmol ZnO, 300° C, the filling rate of 35%, and over 30% starting from fructose at the same temperature and filling rate when the reaction time of 40 s and 2.0 mmol ZnO were employed. The collaborative effects of ZnO and NaOH used as the catalysts together at the same time were also studied. Furthermore, the catalytic mechanism of ZnO in the hydrothermal conversion of carbohydrates into lactic acid was discussed.

Interrogating the catalytic mechanism of nanoparticle mediated Stille coupling reactions employing bio-inspired Pd nanocatalysts.

PubMed

Pacardo, Dennis B; Slocik, Joseph M; Kirk, Kyle C; Naik, Rajesh R; Knecht, Marc R

2011-05-01

To address issues concerning the global environmental and energy state, new catalytic technologies must be developed that translate ambient and efficient conditions to heavily used reactions. To achieve this, the structure/function relationship between model catalysts and individual reactions must be critically discerned to identify structural motifs responsible for the reactivity. This is especially true for nanoparticle-based systems where this level of information remains limited. Here we present evidence indicating that peptide-capped Pd nanoparticles drive Stille C-C coupling reactions via Pd atom leaching. Through a series of reaction studies, the materials are shown to be optimized for reactivity under ambient conditions where increases in temperature or catalyst concentration deactivate reactivity due to the leaching process. A quartz crystal microbalance analysis demonstrates that Pd leaching occurs during the initial oxidative addition step at the nanoparticle surface by aryl halides. Together, this suggests that peptide-based materials may be optimally suited for use as model systems to isolate structural motifs responsible for the generation of catalytically reactive materials under ambient synthetic conditions. © The Royal Society of Chemistry 2011

Interrogating the catalytic mechanism of nanoparticle mediated Stille coupling reactions employing bio-inspired Pd nanocatalysts

NASA Astrophysics Data System (ADS)

Pacardo, Dennis B.; Slocik, Joseph M.; Kirk, Kyle C.; Naik, Rajesh R.; Knecht, Marc R.

2011-05-01

To address issues concerning the global environmental and energy state, new catalytic technologies must be developed that translate ambient and efficient conditions to heavily used reactions. To achieve this, the structure/function relationship between model catalysts and individual reactions must be critically discerned to identify structural motifs responsible for the reactivity. This is especially true for nanoparticle-based systems where this level of information remains limited. Here we present evidence indicating that peptide-capped Pd nanoparticles drive Stille C-C coupling reactions via Pd atom leaching. Through a series of reaction studies, the materials are shown to be optimized for reactivity under ambient conditions where increases in temperature or catalyst concentration deactivate reactivity due to the leaching process. A quartz crystal microbalance analysis demonstrates that Pd leaching occurs during the initial oxidative addition step at the nanoparticle surface by aryl halides. Together, this suggests that peptide-based materials may be optimally suited for use as model systems to isolate structural motifs responsible for the generation of catalytically reactive materials under ambient synthetic conditions.

Active avoidance learning requires prefrontal suppression of amygdala-mediated defensive reactions.

PubMed

Moscarello, Justin M; LeDoux, Joseph E

2013-02-27

Signaled active avoidance (AA) paradigms train subjects to prevent an aversive outcome by performing a learned behavior during the presentation of a conditioned cue. This complex form of conditioning involves pavlovian and instrumental components, which produce competing behavioral responses that must be reconciled for the subject to successfully avoid an aversive stimulus. In signaled AA paradigm for rat, we tested the hypothesis that the instrumental component of AA training recruits infralimbic prefrontal cortex (ilPFC) to inhibit central amygdala (CeA)-mediated Pavlovian reactions. Pretraining lesions of ilPFC increased conditioned freezing while causing a corresponding decrease in avoidance; lesions of CeA produced opposite effects, reducing freezing and facilitating avoidance behavior. Pharmacological inactivation experiments demonstrated that ilPFC is relevant to both acquisition and expression phases of AA learning. Inactivation experiments also revealed that AA produces an ilPFC-mediated diminution of pavlovian reactions that extends beyond the training context, even when the conditioned stimulus is presented in an environment that does not allow the avoidance response. Finally, injection of a protein synthesis inhibitor into either ilPFC or CeA impaired or facilitated AA, respectively, showing that avoidance training produces two opposing memory traces in these regions. These data support a model in which AA learning recruits ilPFC to inhibit CeA-mediated defense behaviors, leading to a robust suppression of freezing that generalizes across environments. Thus, ilPFC functions as an inhibitory interface, allowing instrumental control over an aversive outcome to attenuate the expression of freezing and other reactions to conditioned threat.

Radical-Mediated Reactions of α-Bromo Aluminium Thioacetals, α-Bromothioesters, and Xanthates for Thiolactone Synthesis.

PubMed

McCourt, Ruairí O; Dénès, Fabrice; Scanlan, Eoin M

2018-04-13

Thiolactones have attracted considerable attention in recent years as bioactive natural products, lead compounds for drug discovery, molecular probes, and reagents for polymerisation. We have investigated radical-mediated C-C bond forming reactions as a strategy for thiolactone synthesis. Cyclisation of an α-bromo aluminium thioacetal was investigated under radical conditions. It was found that at low temperature, a radical fragmentation and rearrangement process occurs. A putative reaction mechanism involving a previously unreported aluminium templated thiol-ene step for the rearrangement process is presented. Cyclisation reactions of α-bromo thioesters and α-xanthate thioesters under radical mediated conditions furnished the desired thiolactones in moderate yields.

Application of alkyne-TCNQ addition reaction to polymerization.

PubMed

Washino, Yusuke; Michinobu, Tsuyoshi

2011-04-19

The polymerization using a high-yielding addition reaction between electron-rich alkynes and 7,7,8,8-tetracyanoquinodimethane (TCNQ) derivatives is described. The bifunctional monomer containing two TCNQ moieties and the counter comonomer bearing two dialkylaniline (DAA)-substituted alkynes are reacted in 1,2-dichloroethane under mild heating conditions. At the high monomer concentrations, high molecular weight linear polymers are obtained, while the reaction at the low monomer concentrations produces a significant amount of the cyclic compounds. A clear relationship between the monomer concentration and the cyclic compound amount is demonstrated. The obtained polymers feature a sufficient thermal stability with the decomposition temperature exceeding 300  °C as well as strong charge-transfer (CT) bands and redox activities ascribed to the produced donor-acceptor moieties. These features are also used to optimize the polymerization conditions and to estimate the chemical structures. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High temperature chemical kinetic study of the H2-CO-CO2-NO reaction system

NASA Technical Reports Server (NTRS)

Jachimowski, C. J.

1975-01-01

An experimental study of the kinetics of the H2-CO-CO2-NO reaction system was made behind incident shock waves at temperatures of 2460 and 2950 K. The overall rate of the reaction was measured by monitoring radiation from the CO + O yields CO2 + h upoilon reaction. Correlation of these data with a detailed reaction mechanism showed that the high-temperature rate of the reaction N + OH yields NO + H can be described by the low-temperature (320 K) rate coefficient. Catalytic dissociation of molecular hydrogen was an important reaction under the tests conditions.

Design, development, and demonstration of a fully LabVIEW controlled in situ electrochemical Fourier transform infrared setup combined with a wall-jet electrode to investigate the electrochemical interface of nanoparticulate electrocatalysts under reaction conditions.

PubMed

Nesselberger, Markus; Ashton, Sean J; Wiberg, Gustav K H; Arenz, Matthias

2013-07-01

We present a detailed description of the construction of an in situ electrochemical ATR-FTIR setup combined with a wall-jet electrode to investigate the electrocatalytic properties of nanoparticulate catalysts in situ under controlled mass transport conditions. The presented setup allows the electrochemical interface to be probed in combination with the simultaneous determination of reaction rates. At the same time, the high level of automation allows it to be used as a standard tool in electrocatalysis research. The performance of the setup was demonstrated by probing the oxygen reduction reaction on a platinum black catalyst in sulfuric electrolyte.

Regulation of cutaneous allergic reaction by odorant inhalation.

PubMed

Hosoi, J; Tsuchiya, T

2000-03-01

Olfactory stimuli modulate emotional conditions and the whole body immune system. Effects of odorant inhalation on cutaneous immune reaction were examined. Contact hypersensitivity to 2,4, 6-trinitrochlorobenzene was elicited in C57BL/6 mice. The reaction was suppressed at both the induction and elicitation phases by exposure to an odorant, citralva. Topical application of citralva or lyral/lilial did not affect the reaction. The suppressive effect of citralva was more potent than that of another odorant, lyral/lilial. Citralva decreased the number of epidermal Langerhans cells, whereas lyral/lilial had a weak effect. Citralva but not lyral/lilial induced plasma corticosterone. Glucocorticoid receptor antagonist abrogated the suppressive effect of citralva on contact hypersensitivity. Serum interleukin-12 was downregulated by exposure to citralva or lyral/lilial. These data demonstrate that olfactory stimuli regulate the cutaneous immune system.

Extent of reaction in open systems with multiple heterogeneous reactions

USGS Publications Warehouse

Friedly, John C.

1991-01-01

The familiar batch concept of extent of reaction is reexamined for systems of reactions occurring in open systems. Because species concentrations change as a result of transport processes as well as reactions in open systems, the extent of reaction has been less useful in practice in these applications. It is shown that by defining the extent of the equivalent batch reaction and a second contribution to the extent of reaction due to the transport processes, it is possible to treat the description of the dynamics of flow through porous media accompanied by many chemical reactions in a uniform, concise manner. This approach tends to isolate the reaction terms among themselves and away from the model partial differential equations, thereby enabling treatment of large problems involving both equilibrium and kinetically controlled reactions. Implications on the number of coupled partial differential equations necessary to be solved and on numerical algorithms for solving such problems are discussed. Examples provided illustrate the theory applied to solute transport in groundwater flow.

[Sense of coherence (SOC), occupational stress reactions, and the relationship of SOC with occupational stress reactions among male nurses working in a hospital].

PubMed

Yoshida, Eri; Yamada, Kazuko; Morioka, Ikuharu

2014-01-01

There is limited information about the sense of coherence (SOC), stress reactions and the relationship between SOC and stress reactions in male nurses. The aim of this survey was to clarify SOC, stress reactions, and the relationship of SOC with stress reactions in male nurses working in a hospital. Fifty-one male and 51 female nurses took part in a questionnaire survey. Each female subject was matched with a male of the same age (within 1 year), qualifications (nurse only or both nurse and public health nurse), and work place (internal medicine ward, surgery ward or others). The question items were basic attributes, SOC, Brief Job Stress Questionnaire and Brief Scales for Coping Profile (BSCP). To examine the relationship between the SOC and stress reactions, a multiple regression analysis was performed with psychological or somatic symptoms, as the dependent variable. The median age of male nurses was 27 (interquartile range: 24-30) years. The median length of their working career was 4 (2-7) years. There were no gender differences in the total scores of SOC. Among the stressors, the conditions of mental demand were better in male nurses, but the conditions of stress by workplace environment were worse than in female nurses. Depressive mood, one of the stress reactions, was worse in male nurses. Support from supervisors and coworkers that had an effect on stress reactions were weaker in male nurses than in female nurses. In the subscales of BSCP, "emotional expression to others" and "avoidance and suppression" were more often used by male nurses, but "seeking help for a solution to problems" was less frequently used by them than by female nurses. There were significant relationships between the total score of SOC and psychological and somatic symptoms in both sexes, even when adjusted for 9 stressor factors, 4 factors that had an effect on stress reactions, and 6 subscales of the BSCP and age. The sense of manageability, one of the subscales of SOC, showed

ReactionMap: an efficient atom-mapping algorithm for chemical reactions.

PubMed

Fooshee, David; Andronico, Alessio; Baldi, Pierre

2013-11-25

Large databases of chemical reactions provide new data-mining opportunities and challenges. Key challenges result from the imperfect quality of the data and the fact that many of these reactions are not properly balanced or atom-mapped. Here, we describe ReactionMap, an efficient atom-mapping algorithm. Our approach uses a combination of maximum common chemical subgraph search and minimization of an assignment cost function derived empirically from training data. We use a set of over 259,000 balanced atom-mapped reactions from the SPRESI commercial database to train the system, and we validate it on random sets of 1000 and 17,996 reactions sampled from this pool. These large test sets represent a broad range of chemical reaction types, and ReactionMap correctly maps about 99% of the atoms and about 96% of the reactions, with a mean time per mapping of 2 s. Most correctly mapped reactions are mapped with high confidence. Mapping accuracy compares favorably with ChemAxon's AutoMapper, versions 5 and 6.1, and the DREAM Web tool. These approaches correctly map 60.7%, 86.5%, and 90.3% of the reactions, respectively, on the same data set. A ReactionMap server is available on the ChemDB Web portal at http://cdb.ics.uci.edu .

Modular verification of chemical reaction network encodings via serializability analysis

PubMed Central

Lakin, Matthew R.; Stefanovic, Darko; Phillips, Andrew

2015-01-01

Chemical reaction networks are a powerful means of specifying the intended behaviour of synthetic biochemical systems. A high-level formal specification, expressed as a chemical reaction network, may be compiled into a lower-level encoding, which can be directly implemented in wet chemistry and may itself be expressed as a chemical reaction network. Here we present conditions under which a lower-level encoding correctly emulates the sequential dynamics of a high-level chemical reaction network. We require that encodings are transactional, such that their execution is divided by a “commit reaction” that irreversibly separates the reactant-consuming phase of the encoding from the product-generating phase. We also impose restrictions on the sharing of species between reaction encodings, based on a notion of “extra tolerance”, which defines species that may be shared between encodings without enabling unwanted reactions. Our notion of correctness is serializability of interleaved reaction encodings, and if all reaction encodings satisfy our correctness properties then we can infer that the global dynamics of the system are correct. This allows us to infer correctness of any system constructed using verified encodings. As an example, we show how this approach may be used to verify two- and four-domain DNA strand displacement encodings of chemical reaction networks, and we generalize our result to the limit where the populations of helper species are unlimited. PMID:27325906

Role of the Support and Reaction Conditions on the Vapor-Phase Deoxygenation of m-Cresol over Pt/C and Pt/TiO 2 Catalysts

DOE PAGES

Griffin, Michael B.; Ferguson, Glen A.; Ruddy, Daniel A.; ...

2016-03-23

The catalytic deoxygenation of biomass fast pyrolysis vapors offers a promising route for the sustainable production of liquid transportation fuels. However, a clear understanding of the mechanistic details involved in this process has yet to be achieved, and questions remain regarding the role of the catalyst support and the influence of reaction conditions. In order to gain insight into these questions, the deoxygenation of m-cresol was investigated over Pt/C and Pt/TiO 2 catalysts using experimental and computational techniques. The performance of each catalyst was evaluated in a packed-bed reactor under two conditions (523 K, 2.0 MPa and 623 K, 0.5more » MPa), and the energetics of the ring hydrogenation, direct deoxygenation, and tautomerization mechanisms were calculated over hydrogen-covered Pt(111) and oxygen vacancies on the surface of TiO 2(101). Over Pt(111), ring hydrogenation to 3-methylcyclohexanone and 3-methylcyclohexanol was found to be the most energetically favorable pathway. Over TiO 2(101), tautomerization and direct deoxygenation to toluene were identified as additional energetically favorable routes. These calculations are consistent with the experimental data, in which Pt/TiO 2 was more active on a metal site basis and exhibited higher selectivity to toluene at 623 K relative to Pt/C. On the basis of these results, it is likely that the reactivity of Pt/TiO 2 and Pt/C is driven by the metallic phase at 523 K, while contributions from the TiO 2 support enhance deoxygenation at 623 K. These results highlight the synergistic effects between hydrogenation catalysts and reducible metal oxide supports and provide insight into the reaction pathways responsible for their enhanced deoxygenation performance.« less

Elementary Chemical Reactions in Surface Photocatalysis

NASA Astrophysics Data System (ADS)

Guo, Qing; Zhou, Chuanyao; Ma, Zhibo; Ren, Zefeng; Fan, Hongjun; Yang, Xueming

2018-04-01

Photocatalytic hydrogen evolution and organic degradation on oxide materials have been extensively investigated in the last two decades. Great efforts have been dedicated to the study of photocatalytic reaction mechanisms of a variety of molecules on TiO2 surfaces by using surface science methods under ultra-high vacuum (UHV) conditions, providing fundamental understanding of surface chemical reactions in photocatalysis. In this review, we summarize the recent progress in the study of photocatalysis of several important species (water, methanol, and aldehydes) on different TiO2 surfaces. The results of these studies have provided us deep insights into the elementary processes of surface photocatalysis and stimulated a new frontier of research in this area. Based on the results of these studies, a new dynamics-based photocatalysis model is also discussed.

A General Synthetic Route to Polycyclic Aromatic Dicarboximides by Palladium-Catalyzed Annulation Reaction.

PubMed

Shoyama, Kazutaka; Mahl, Magnus; Seifert, Sabine; Würthner, Frank

2018-03-20

Here we report a general method for the synthesis of polycyclic aromatic dicarboximides (PADIs) by palladium-catalyzed annulation of naphthalene dicarboximide to different types of aromatic substrates. Reaction conditions were optimized by systematic variation of ligand, solvent, and additive. It was shown that solvent has a decisive effect on the yield of the reaction products, and thus 1-chloronaphthalene as solvent afforded the highest yield. By applying the optimized reaction conditions, a broad series of planar carbo- and heterocycle containing PADIs were synthesized in up to 97% yield. Moreover, this approach could be applied to curved aromatic scaffold to achieve the respective bowl-shaped PADI. Two-fold annulation was accomplished by employing arene diboronic esters, affording polycyclic aromatic bis(dicarboximides). The optical and electrochemical properties of this broad series of PADIs were explored as well.

A Laboratory Test Setup for in Situ Measurements of the Dielectric Properties of Catalyst Powder Samples under Reaction Conditions by Microwave Cavity Perturbation: Set up and Initial Tests

PubMed Central

Dietrich, Markus; Rauch, Dieter; Porch, Adrian; Moos, Ralf

2014-01-01

The catalytic behavior of zeolite catalysts for the ammonia-based selective catalytic reduction (SCR) of nitrogen oxides (NOX) depends strongly on the type of zeolite material. An essential precondition for SCR is a previous ammonia gas adsorption that occurs on acidic sites of the zeolite. In order to understand and develop SCR active materials, it is crucial to know the amount of sorbed ammonia under reaction conditions. To support classical temperature-programmed desorption (TPD) experiments, a correlation of the dielectric properties with the catalytic properties and the ammonia sorption under reaction conditions appears promising. In this work, a laboratory test setup, which enables direct measurements of the dielectric properties of catalytic powder samples under a defined gas atmosphere and temperature by microwave cavity perturbation, has been developed. Based on previous investigations and computational simulations, a resonator cavity and a heating system were designed, installed and characterized. The resonator cavity is designed to operate in its TM010 mode at 1.2 GHz. The first measurement of the ammonia loading of an H-ZSM-5 zeolite confirmed the operating performance of the test setup at constant temperatures of up to 300 °C. It showed how both real and imaginary parts of the relative complex permittivity are strongly correlated with the mass of stored ammonia. PMID:25211199

Does Observation of Postural Imbalance Induce a Postural Reaction?

PubMed Central

Tia, Banty; Saimpont, Arnaud; Paizis, Christos; Mourey, France; Fadiga, Luciano; Pozzo, Thierry

2011-01-01

Background Several studies bring evidence that action observation elicits contagious responses during social interactions. However automatic imitative tendencies are generally inhibited and it remains unclear in which conditions mere action observation triggers motor behaviours. In this study, we addressed the question of contagious postural responses when observing human imbalance. Methodology/Principal Findings We recorded participants' body sway while they observed a fixation cross (control condition), an upright point-light display of a gymnast balancing on a rope, and the same point-light display presented upside down. Our results showed that, when the upright stimulus was displayed prior to the inverted one, centre of pressure area and antero-posterior path length were significantly greater in the upright condition compared to the control and upside down conditions. Conclusions/Significance These results demonstrate a contagious postural reaction suggesting a partial inefficiency of inhibitory processes. Further, kinematic information was sufficient to trigger this reaction. The difference recorded between the upright and upside down conditions indicates that the contagion effect was dependent on the integration of gravity constraints by body kinematics. Interestingly, the postural response was sensitive to habituation, and seemed to disappear when the observer was previously shown an inverted display. The motor contagion recorded here is consistent with previous work showing vegetative output during observation of an effortful movement and could indicate that lower level control facilitates contagion effects. PMID:21423622

Chemical computing with reaction-diffusion processes.

PubMed

Gorecki, J; Gizynski, K; Guzowski, J; Gorecka, J N; Garstecki, P; Gruenert, G; Dittrich, P

2015-07-28

Chemical reactions are responsible for information processing in living organisms. It is believed that the basic features of biological computing activity are reflected by a reaction-diffusion medium. We illustrate the ideas of chemical information processing considering the Belousov-Zhabotinsky (BZ) reaction and its photosensitive variant. The computational universality of information processing is demonstrated. For different methods of information coding constructions of the simplest signal processing devices are described. The function performed by a particular device is determined by the geometrical structure of oscillatory (or of excitable) and non-excitable regions of the medium. In a living organism, the brain is created as a self-grown structure of interacting nonlinear elements and reaches its functionality as the result of learning. We discuss whether such a strategy can be adopted for generation of chemical information processing devices. Recent studies have shown that lipid-covered droplets containing solution of reagents of BZ reaction can be transported by a flowing oil. Therefore, structures of droplets can be spontaneously formed at specific non-equilibrium conditions, for example forced by flows in a microfluidic reactor. We describe how to introduce information to a droplet structure, track the information flow inside it and optimize medium evolution to achieve the maximum reliability. Applications of droplet structures for classification tasks are discussed. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

Reaction norm model to describe environmental sensitivity across first lactation in dairy cattle under tropical conditions.

PubMed

Bignardi, Annaiza Braga; El Faro, Lenira; Pereira, Rodrigo Junqueira; Ayres, Denise Rocha; Machado, Paulo Fernando; de Albuquerque, Lucia Galvão; Santana, Mário Luiz

2015-10-01

Reaction norm models have been widely used to study genotype by environment interaction (G × E) in animal breeding. The objective of this study was to describe environmental sensitivity across first lactation in Brazilian Holstein cows using a reaction norm approach. A total of 50,168 individual monthly test day (TD) milk yields (10 test days) from 7476 complete first lactations of Holstein cattle were analyzed. The statistical models for all traits (10 TDs and for 305-day milk yield) included the fixed effects of contemporary group, age of cow (linear and quadratic effects), and days in milk (linear effect), except for 305-day milk yield. A hierarchical reaction norm model (HRNM) based on the unknown covariate was used. The present study showed the presence of G × E in milk yield across first lactation of Holstein cows. The variation in the heritability estimates implies differences in the response to selection depending on the environment where the animals of this population are evaluated. In the average environment, the heritabilities for all traits were rather similar, in range from 0.02 to 0.63. The scaling effect of G × E predominated throughout most of lactation. Particularly during the first 2 months of lactation, G × E caused reranking of breeding values. It is therefore important to include the environmental sensitivity of animals according to the phase of lactation in the genetic evaluations of Holstein cattle in tropical environments.

Studies of Hydrogen Production by the Water Gas Shift Reaction and Related Chemistry

DTIC Science & Technology

1983-04-15

HYDROGEN PRODUCTION BY THE WATER GAS SHIFT REACTION AND RELATED CHEMISTRY Institution: The University of Rochester Department of Chemistry -. Rochester...been in siated for the catalysis of the water gas shift reaction, W20 + CO H𔃼 + C02, and for electrocatalytic oxidation of CO, CO + H󈧘 C02 + 2H...particular interest in adopting water gas shift catalysts to act as electrocatalysts for the anode reaction of CO fuel cells. Under these conditions the best

A novel differential electrochemical mass spectrometry method to determine the product distribution from parasitic Methanol oxidation reaction on oxygen reduction reaction catalysts

NASA Astrophysics Data System (ADS)

Jurzinsky, Tilman; Kurzhals, Philipp; Cremers, Carsten

2018-06-01

The oxygen reduction reaction is in research focus since several decades due to its importance for the overall fuel cell performance. In direct methanol fuel cells, the crossover of methanol and its subsequent parasitic oxidation are main issues when it comes to preventing fuel cell performance losses. In this work, we present a novel differential electrochemical mass spectrometry method to evaluate oxygen reduction reaction catalysts on their tolerance to methanol being present at the cathode. Besides this, the setup allows to measure under more realistic fuel cell conditions than typical rotating disc electrode measurements, because the oxygen reduction reaction is evaluated in gaseous phase and a gas diffusion electrode is used as working electrode. Due to the new method, it was possible to investigate the oxygen reduction reaction on two commonly used catalysts (Pt/C and Pt3Co/C) in absence and presence of methanol. It was found, that Pt3Co/C is less prone to parasitic current losses due to methanol oxidation reaction. By connecting a mass spectrometer to the electrochemical cell, the new method allows to determine the products formed on the catalysts due to parasitic methanol electrooxidation.

Observation of the isotope effect in sub-kelvin reactions

NASA Astrophysics Data System (ADS)

Lavert-Ofir, Etay; Shagam, Yuval; Henson, Alon B.; Gersten, Sasha; Kłos, Jacek; Żuchowski, Piotr S.; Narevicius, Julia; Narevicius, Edvardas

2014-04-01

Quantum phenomena in the translational motion of reactants, which are usually negligible at room temperature, can dominate reaction dynamics at low temperatures. In such cold conditions, even the weak centrifugal force is enough to create a potential barrier that keeps reactants separated. However, reactions may still proceed through tunnelling because, at low temperatures, wave-like properties become important. At certain de Broglie wavelengths, the colliding particles can become trapped in long-lived metastable scattering states, leading to sharp increases in the total reaction rate. Here, we show that these metastable states are responsible for a dramatic, order-of-magnitude-strong, quantum kinetic isotope effect by measuring the absolute Penning ionization reaction rates between hydrogen isotopologues and metastable helium down to 0.01 K. We demonstrate that measurements of a single isotope are insufficient to constrain ab initio calculations, making the kinetic isotope effect in the cold regime necessary to remove ambiguity among possible potential energy surfaces.

Gas-Phase Formation Rates of Nitric Acid and Its Isomers Under Urban Conditions

NASA Technical Reports Server (NTRS)

Okumura, M.; Mollner, A. K.; Fry, J. L.; Feng, L.

2005-01-01

Ozone formation in urban smog is controlled by a complex set of reactions which includes radical production from photochemical processes, catalytic cycles which convert NO to NO2, and termination steps that tie up reactive intermediates in long-lived reservoirs. The reaction OH + NO2 + M -4 HONO2 + M (la) is a key termination step because it transforms two short-lived reactive intermediates, OH and NO2, into relatively long-lived nitric acid. Under certain conditions (low VOC/NOx), ozone production in polluted urban airsheds can be highly sensitive to this reaction, but the rate parameters are not well constrained. This report summarizes the results of new laboratory studies of the OH + NO2 + M reaction including direct determination of the overall rate constant and branching ratio for the two reaction channels under atmospherically relevant conditions.

Possibilities of production of transfermium nuclei in complete fusion reactions with radioactive beams

NASA Astrophysics Data System (ADS)

Hong, Juhee; Adamian, G. G.; Antonenko, N. V.

2017-07-01

The possibilities of direct production of new isotopes of transfermium nuclei 261,263,264No, 264Lr263, 263,264,266,268Rf, 265Db264, and 267,268,270,272Sg are studied in various asymmetric hot fusion-evaporation reactions with radioactive beams. The optimal reaction partners and conditions for the synthesis of new isotopes are suggested. The products of the suggested reactions can fill a gap of unknown isotopes between the isotopes of heaviest nuclei obtained in the x n evaporation channels of the cold and hot complete fusion reactions with the stable beams.

Reactions of butadiyne. 1: The reaction with hydrogen atoms

NASA Technical Reports Server (NTRS)

Schwanebeck, W.; Warnatz, J.

1984-01-01

The reaction of hydrogen (H) atoms with butadiene (C4H2) was studied at room temperature in a pressure range between w mbar and 10 mbar. The primary step was an addition of H to C4H2 which is in its high pressure range at p 1 mbar. Under these conditions the following addition of a second H atom lies in the transition region between low and high pressure range. Vibrationally excited C4H4 can be deactivated to form buten-(1)-yne-(3)(C4H4) or decomposes into two C2H2 molecules. The rate constant at room temperature for primary step is given. The second order rate constant for the consumption of buten-(1)-yne-(3) is an H atom excess at room temperature is given.

Coke formation and carbon atom economy of methanol-to-olefins reaction.

PubMed

Wei, Yingxu; Yuan, Cuiyu; Li, Jinzhe; Xu, Shutao; Zhou, You; Chen, Jingrun; Wang, Quanyi; Xu, Lei; Qi, Yue; Zhang, Qing; Liu, Zhongmin

2012-05-01

The methanol-to-olefins (MTO) process is becoming the most important non-petrochemical route for the production of light olefins from coal or natural gas. Maximizing the generation of the target products, ethene and propene, and minimizing the production of byproducts and coke, are major considerations in the efficient utilization of the carbon resource of methanol. In the present work, the heterogeneous catalytic conversion of methanol was evaluated by performing simultaneous measurements of the volatile products generated in the gas phase and the confined coke deposition in the catalyst phase. Real-time and complete reaction profiles were plotted to allow the comparison of carbon atom economy of methanol conversion over the catalyst SAPO-34 at varied reaction temperatures. The difference in carbon atom economy was closely related with the coke formation in the SAPO-34 catalyst. The confined coke compounds were determined. A new type of confined organics was found, and these accounted for the quick deactivation and low carbon atom economy under low-reaction-temperature conditions. Based on the carbon atom economy evaluation and coke species determination, optimized operating conditions for the MTO process are suggested; these conditions guarantee high conversion efficiency of methanol. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reaction Extrema: Extent of Reaction in General Chemistry

ERIC Educational Resources Information Center

Vandezande, Jonathon E.; Vander Griend, Douglas A.; DeKock, Roger L.

2013-01-01

Nearly 100 years ago de Donder introduced the term "extent of reaction", ?. We build on that work by defining the concept of reagent extrema for an arbitrary chemical reaction, aA + bB [reversible reaction] yY + zZ. The central equation is ?^[subscript i] = -n[subscript i,0]/?[subscript i]. The symbol ?^[subscript i] represents the…

One-pot reaction for the preparation of biofunctionalized self-assembled monolayers on gold surfaces

NASA Astrophysics Data System (ADS)

Raigoza, Annette F.; Fies, Whitney; Lim, Amber; Onyirioha, Kristeen; Webb, Lauren J.

2017-02-01

The Huisgen cycloaddition reaction (;click; chemistry) has been used extensively to functionalize surfaces with macromolecules in a straightforward manner. We have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to a well-ordered azide-terminated alkanethiol self-assembled monolayer (SAM) on a Au(111) surface. While convenient, click-based strategies potentially pose significant problems from reagents, solvents, and reaction temperatures that may irreversibly damage some molecules or substrates. Tuning click chemistry conditions would allow individual optimization of reaction conditions for a wide variety of biomolecules and substrate materials. Here, we explore the utility of simultaneous SAM formation and peptide-attachment chemistry in a one-pot reaction. We demonstrate that a formerly multistep reaction can be successfully carried out concurrently by mixing azide-terminated alkanethiols, CuCl, and a propargylglycine-containing peptide over a bare gold surface in ethanol and reacting at 70 °C. X-ray photoelectron spectroscopy (XPS), surface infrared spectroscopy, surface circular dichroic (CD) spectroscopy, and scanning tunneling microscopy (STM) were used to determine that this one-pot reaction strategy resulted in a high density of surface-bound α-helices without aggregation. This work demonstrates the simplicity and versatility of a SAM-plus-click chemistry strategy for functionalizing Au surfaces with structured biomolecules.

A quantum chemical study for the multichannel reaction PH 2 + PH 2

NASA Astrophysics Data System (ADS)

Pimentel, André S.; Viana, Rommel B.

2007-04-01

The PH 2 + PH 2 multichannel reaction path was proposed in this study. The transition state that connects the reactants to cis-P 2H 2 isomer was found for the first time ever. This process is not allowed to occur at ordinary conditions because of its high energy barrier, 70 kcal mol -1. The PH 2 + PH 2 disproportionation to form the triplet PH 3 radical is an exothermic and spontaneous reaction. The PH 2 + PH 2 reaction may also form the P 2H 4 molecule in the absence of surfaces.

Leprosy reactions in postelimination stage: the Bangladesh experience.

PubMed

Mowla, M R; Ara, S; Mizanur Rahman, A F M; Tripura, S P; Paul, S

2017-04-01

Leprosy reactions are immunologically mediated conditions and a major cause of disability before, during and after multidrug therapy (MDT). Little data have been published on the epidemiology of leprosy reactions in Bangladesh. To describe the pattern and prevalence of leprosy reactions in the postelimination stage. A descriptive retrospective cross-sectional study was carried out in Chittagong Medical College Hospital using the registered records of patients in the period between 2004 and 2013. Of the 670 patients with leprosy, 488 (73.38%) were males and 182 (27.37%) were females. The prevalence of reaction was in 300 (44.78%) patients with a male:female ratio of 3.55 : 1. The age-specific cumulative reaction cases at >40 years were 115 (38.33%) among all age groups. The prevalence of reaction was found to be in 166 (55.33%) patients for the reversal reaction, 49 (16.57%) for the erythema nodosum leprosum (ENL) and 85 (28.33%) for the neuritis. Borderline tuberculoid was most common (106, 35.33%)in the reversal reaction group, while lepromatous leprosy was most common (37, 12.33%) in ENL group. More than half of the patients (169, 56.33%) had reactions at the time of presentations, while 85 (28.33%) and 46 (15.33%) patients developed reaction during and after MDT, respectively. The reversal reaction group presented with ≥six skin lesions in 96 (57.83%) patients and ≥two nerve function impairments (NFIs) in 107 (64.46%) patients. The ENL was present chiefly as papulo-nodular lesions in 45 (91.84%) patients followed by pustule-necrotic lesions in four (8.16%), neuritis in 33 (67.35%), fever in 24 (48.98%), lymphadenitis in six (12.24%), arthritis in five (10.20%) and iritis in two (4.08%). Bacterial index ≥3 had been demonstrated in 34 (60.71%) patients in ENL group. The incidence of leprosy reaction seemed to be more than three times common in borderline tuberculoid (52.33%) group than in lepromatous leprosy (14%) group. Reactions with NFI and disability

Aza-crown ether complex cation ionic liquids: preparation and applications in organic reactions.

PubMed

Song, Yingying; Cheng, Chen; Jing, Huanwang

2014-09-26

Aza-crown ether complex cation ionic liquids (aCECILs) were devised, fabricated, and characterized by using NMR spectroscopy, MS, thermogravimetric differential thermal analysis (TG-DTA), elemental analysis and physical properties. These new and room-temperature ILs were utilized as catalysts in various organic reactions, such as the cycloaddition reaction of CO2 to epoxides, esterification of acetic acid and alcohols, the condensation reaction of aniline and propylene carbonate, and Friedel-Crafts alkylation of indole with aldehydes were investigated carefully. In these reactions, the ionic liquid exhibited cooperative catalytic activity between the anion and cation. In addition, the aza-[18-C-6HK][HSO4]2 was the best acidic catalyst in the reactions of esterification and Friedel-Crafts alkylation under mild reaction conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimization of Maillard Reaction in Model System of Glucosamine and Cysteine Using Response Surface Methodology

PubMed Central

Arachchi, Shanika Jeewantha Thewarapperuma; Kim, Ye-Joo; Kim, Dae-Wook; Oh, Sang-Chul; Lee, Yang-Bong

2017-01-01

Sulfur-containing amino acids play important roles in good flavor generation in Maillard reaction of non-enzymatic browning, so aqueous model systems of glucosamine and cysteine were studied to investigate the effects of reaction temperature, initial pH, reaction time, and concentration ratio of glucosamine and cysteine. Response surface methodology was applied to optimize the independent reaction parameters of cysteine and glucosamine in Maillard reaction. Box-Behnken factorial design was used with 30 runs of 16 factorial levels, 8 axial levels and 6 central levels. The degree of Maillard reaction was determined by reading absorption at 425 nm in a spectrophotometer and Hunter’s L, a, and b values. ΔE was consequently set as the fifth response factor. In the statistical analyses, determination coefficients (R2) for their absorbance, Hunter’s L, a, b values, and ΔE were 0.94, 0.79, 0.73, 0.96, and 0.79, respectively, showing that the absorbance and Hunter’s b value were good dependent variables for this model system. The optimum processing parameters were determined to yield glucosamine-cysteine Maillard reaction product with higher absorbance and higher colour change. The optimum estimated absorbance was achieved at the condition of initial pH 8.0, 111°C reaction temperature, 2.47 h reaction time, and 1.30 concentration ratio. The optimum condition for colour change measured by Hunter’s b value was 2.41 h reaction time, 114°C reaction temperature, initial pH 8.3, and 1.26 concentration ratio. These results can provide the basic information for Maillard reaction of aqueous model system between glucosamine and cysteine. PMID:28401086

Optimization of Maillard Reaction in Model System of Glucosamine and Cysteine Using Response Surface Methodology.

PubMed

Arachchi, Shanika Jeewantha Thewarapperuma; Kim, Ye-Joo; Kim, Dae-Wook; Oh, Sang-Chul; Lee, Yang-Bong

2017-03-01

Sulfur-containing amino acids play important roles in good flavor generation in Maillard reaction of non-enzymatic browning, so aqueous model systems of glucosamine and cysteine were studied to investigate the effects of reaction temperature, initial pH, reaction time, and concentration ratio of glucosamine and cysteine. Response surface methodology was applied to optimize the independent reaction parameters of cysteine and glucosamine in Maillard reaction. Box-Behnken factorial design was used with 30 runs of 16 factorial levels, 8 axial levels and 6 central levels. The degree of Maillard reaction was determined by reading absorption at 425 nm in a spectrophotometer and Hunter's L, a, and b values. ΔE was consequently set as the fifth response factor. In the statistical analyses, determination coefficients (R 2 ) for their absorbance, Hunter's L, a, b values, and ΔE were 0.94, 0.79, 0.73, 0.96, and 0.79, respectively, showing that the absorbance and Hunter's b value were good dependent variables for this model system. The optimum processing parameters were determined to yield glucosamine-cysteine Maillard reaction product with higher absorbance and higher colour change. The optimum estimated absorbance was achieved at the condition of initial pH 8.0, 111°C reaction temperature, 2.47 h reaction time, and 1.30 concentration ratio. The optimum condition for colour change measured by Hunter's b value was 2.41 h reaction time, 114°C reaction temperature, initial pH 8.3, and 1.26 concentration ratio. These results can provide the basic information for Maillard reaction of aqueous model system between glucosamine and cysteine.

Acridine orange staining reaction as an index of physiological activity in Escherichia coli

NASA Technical Reports Server (NTRS)

McFeters, G. A.; Singh, A.; Byun, S.; Callis, P. R.; Williams, S.

1991-01-01

The assumption that the acridine orange (AO) color reaction may be used as an index of physiological activity was investigated in laboratory grown Escherichia coli. Spectrofluorometric observations of purified nucleic acids, ribosomes and the microscopic color of bacteriophage-infected cells stained with AO confirmed the theory that single-stranded nucleic acids emit orange to red fluorescence while those that are double-stranded fluoresce green in vivo. Bacteria growing actively in a rich medium could be distinguished from cells in stationary phase by the AO reaction. Cells from log phase appeared red, whereas those in stationary phase were green. However, this differentiation was not seen when the bacteria were grown in a minimal medium or when a variation of the staining method was used. Also, shifting bacteria in stationary phase to starvation conditions rapidly changed their AO staining reaction. Boiling and exposure to lethal concentrations of azide and formalin resulted in stationary-phase cells that appeared red after staining but bacteria killed with chlorine remained green. These findings indicate that the AO staining reaction may be suggestive of physiological activity under defined conditions. However, variables in staining and fixation procedures as well as uncertainties associated with mixed bacterial populations in environmental samples may produce results that are not consistent with the classical interpretation of this reaction. The importance of validating the putative physiological implications of this staining reaction is stressed.

A Robust and Efficient Method for Steady State Patterns in Reaction-Diffusion Systems

PubMed Central

Lo, Wing-Cheong; Chen, Long; Wang, Ming; Nie, Qing

2012-01-01

An inhomogeneous steady state pattern of nonlinear reaction-diffusion equations with no-flux boundary conditions is usually computed by solving the corresponding time-dependent reaction-diffusion equations using temporal schemes. Nonlinear solvers (e.g., Newton’s method) take less CPU time in direct computation for the steady state; however, their convergence is sensitive to the initial guess, often leading to divergence or convergence to spatially homogeneous solution. Systematically numerical exploration of spatial patterns of reaction-diffusion equations under different parameter regimes requires that the numerical method be efficient and robust to initial condition or initial guess, with better likelihood of convergence to an inhomogeneous pattern. Here, a new approach that combines the advantages of temporal schemes in robustness and Newton’s method in fast convergence in solving steady states of reaction-diffusion equations is proposed. In particular, an adaptive implicit Euler with inexact solver (AIIE) method is found to be much more efficient than temporal schemes and more robust in convergence than typical nonlinear solvers (e.g., Newton’s method) in finding the inhomogeneous pattern. Application of this new approach to two reaction-diffusion equations in one, two, and three spatial dimensions, along with direct comparisons to several other existing methods, demonstrates that AIIE is a more desirable method for searching inhomogeneous spatial patterns of reaction-diffusion equations in a large parameter space. PMID:22773849

Reformulation and solution of the master equation for multiple-well chemical reactions.

PubMed

Georgievskii, Yuri; Miller, James A; Burke, Michael P; Klippenstein, Stephen J

2013-11-21

We consider an alternative formulation of the master equation for complex-forming chemical reactions with multiple wells and bimolecular products. Within this formulation the dynamical phase space consists of only the microscopic populations of the various isomers making up the reactive complex, while the bimolecular reactants and products are treated equally as sources and sinks. This reformulation yields compact expressions for the phenomenological rate coefficients describing all chemical processes, i.e., internal isomerization reactions, bimolecular-to-bimolecular reactions, isomer-to-bimolecular reactions, and bimolecular-to-isomer reactions. The applicability of the detailed balance condition is discussed and confirmed. We also consider the situation where some of the chemical eigenvalues approach the energy relaxation time scale and show how to modify the phenomenological rate coefficients so that they retain their validity.

[Behavioral reactions of animals subjected in the prenatal development period to space flight conditions].

PubMed

Apanasenko, Z I; Kuznetsova, M A; Korotkova, V Iu

1986-01-01

The Wistar female rats were flown on the biosatellite Cosmos-1514 during their pregnancy days 13-18. Offspring (at the age 1 to 3 months) of four of these rats were used to investigate their behavioral reactions in the open field and mazes of different design, food attraction being applied. Control rats of matched pregnancy term were kept either in a vivarium or in a biosatellite mockup where all flight factors, except for weightlessness, were simulated. It was found that exposure to weightlessness in the above intrauterine developmental period caused no serious changes in the behavioral reactions of rats during their postnatal development. The number of refusals and errors and the latency period were similar in the rats from the flight and control groups. Changes were seen only in fine behavioral regulation. The flown animals displayed a lower research activity in the open field, a longer time of search in the maze, a far longer time or grooming and a greater number of inadequate movements, and a stronger response to external inhibiting stimuli. These changes seem to be caused by a slight attenuation of the basic nervous processes (primarily, inhibitory) and a decrease of their balance and lability. These effects may be associated with an inhibitory influence of space flight factors on the maturation of cortical structures.

Identification of reaction products from reactions of free chlorine with the lipid-regulator gemfibrozil.

PubMed

Krkošek, Wendy H; Koziar, Stephen A; White, Robert L; Gagnon, Graham A

2011-01-01

High global consumption rates have led to the occurrence of pharmaceutically active compounds (PhACs) in wastewater. The use of chlorine to disinfect wastewater prior to release into the environment may convert PhACs into uncharacterized chlorinated by-products. In this investigation, chlorination of a common pharmaceutical, the antihyperlipidemic agent gemfibrozil, was documented. Gemfibrozil (2,2-dimethyl-5-(2,5-dimethylphenoxy)pentanoic acid) was reacted with sodium hypochlorite and product formation was monitored by gas chromatography-mass spectrometry (GC-MS). The incorporation of one, two or three chlorine atoms into the aromatic region of gemfibrozil was demonstrated using negative-ion electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS/MS). Further analysis using (1)H nuclear magnetic resonance (NMR) spectroscopy identified the reaction products as 4'-ClGem (5-(4-chloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid) 4',6'-diClGem (5-(4,6-dichloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid), and 3',4',6'-triClGem (5-(3,4,6-trichloro-2,5-dimethylphenoxy)-2,2-dimethylpentanoic acid), products consistent with electrophilic aromatic substitution reactions. The rapid reaction of gemfibrozil with free chlorine at pH conditions relevant to water treatment indicates that a mixture of chlorinated gemfibrozils is likely to be found in wastewater disinfected with chlorine. Copyright © 2010 Elsevier Ltd. All rights reserved.

Coding the Assembly of Polyoxotungstates with a Programmable Reaction System.

PubMed

Ruiz de la Oliva, Andreu; Sans, Victor; Miras, Haralampos N; Long, De-Liang; Cronin, Leroy

2017-05-01

Chemical transformations are normally conducted in batch or flow mode, thereby allowing the chemistry to be temporally or spatially controlled, but these approaches are not normally combined dynamically. However, the investigation of the underlying chemistry masked by the self-assembly processes that often occur in one-pot reactions and exploitation of the potential of complex chemical systems requires control in both time and space. Additionally, maintaining the intermediate constituents of a self-assembled system "off equilibrium" and utilizing them dynamically at specific time intervals provide access to building blocks that cannot coexist under one-pot conditions and ultimately to the formation of new clusters. Herein, we implement the concept of a programmable networked reaction system, allowing us to connect discrete "one-pot" reactions that produce the building block{W 11 O 38 } ≡ {W 11 } under different conditions and control, in real time, the assembly of a series of polyoxometalate clusters {W 12 O 42 } ≡ {W 12 }, {W 22 O 74 } ≡ {W 22 } 1a, {W 34 O 116 } ≡ {W 34 } 2a, and {W 36 O 120 } ≡ {W 36 } 3a, using pH and ultraviolet-visible monitoring. The programmable networked reaction system reveals that is possible to assemble a range of different clusters using {W 11 }-based building blocks, demonstrating the relationship between the clusters within the family of iso-polyoxotungstates, with the final structural motif being entirely dependent on the building block libraries generated in each separate reaction space within the network. In total, this approach led to the isolation of five distinct inorganic clusters using a "fixed" set of reagents and using a fully automated sequence code, rather than five entirely different reaction protocols. As such, this approach allows us to discover, record, and implement complex one-pot reaction syntheses in a more general way, increasing the yield and reproducibility and potentially giving access to

Coding the Assembly of Polyoxotungstates with a Programmable Reaction System

PubMed Central

2017-01-01

Chemical transformations are normally conducted in batch or flow mode, thereby allowing the chemistry to be temporally or spatially controlled, but these approaches are not normally combined dynamically. However, the investigation of the underlying chemistry masked by the self-assembly processes that often occur in one-pot reactions and exploitation of the potential of complex chemical systems requires control in both time and space. Additionally, maintaining the intermediate constituents of a self-assembled system “off equilibrium” and utilizing them dynamically at specific time intervals provide access to building blocks that cannot coexist under one-pot conditions and ultimately to the formation of new clusters. Herein, we implement the concept of a programmable networked reaction system, allowing us to connect discrete “one-pot” reactions that produce the building block{W11O38} ≡ {W11} under different conditions and control, in real time, the assembly of a series of polyoxometalate clusters {W12O42} ≡ {W12}, {W22O74} ≡ {W22} 1a, {W34O116} ≡ {W34} 2a, and {W36O120} ≡ {W36} 3a, using pH and ultraviolet–visible monitoring. The programmable networked reaction system reveals that is possible to assemble a range of different clusters using {W11}-based building blocks, demonstrating the relationship between the clusters within the family of iso-polyoxotungstates, with the final structural motif being entirely dependent on the building block libraries generated in each separate reaction space within the network. In total, this approach led to the isolation of five distinct inorganic clusters using a “fixed” set of reagents and using a fully automated sequence code, rather than five entirely different reaction protocols. As such, this approach allows us to discover, record, and implement complex one-pot reaction syntheses in a more general way, increasing the yield and reproducibility and potentially giving access to nonspecialists. PMID:28414229

Rate and reaction probability of the surface reaction between ozone and dihydromyrcenol measured in a bench scale reactor and a room-sized chamber

NASA Astrophysics Data System (ADS)

Shu, Shi; Morrison, Glenn C.

2012-02-01

Low volatility terpenoids emitted from consumer products can react with ozone on surfaces and may significantly alter concentrations of ozone, terpenoids and reaction products in indoor air. We measured the reaction probability and a second-order surface-specific reaction rate for the ozonation of dihydromyrcenol, a representative indoor terpenoid, adsorbed onto polyvinylchloride (PVC), glass, and latex paint coated spheres. The reaction probability ranged from (0.06-8.97) × 10 -5 and was very sensitive to humidity, substrate and mass adsorbed. The average surface reaction probability is about 10 times greater than that for the gas-phase reaction. The second-order surface-specific rate coefficient ranged from (0.32-7.05) × 10 -15 cm 4 s -1 molecule -1and was much less sensitive to humidity, substrate, or mass adsorbed. We also measured the ozone deposition velocity due to adsorbed dihydromyrcenol on painted drywall in a room-sized chamber, Based on that, we calculated the rate coefficient ((0.42-1.6) × 10 -15 cm 4 molecule -1 s -1), which was consistent with that derived from bench-scale experiments for the latex paint under similar conditions. We predict that more than 95% of dihydromyrcenol oxidation takes place on indoor surfaces, rather than in building air.

Subconscious Visual Cues during Movement Execution Allow Correct Online Choice Reactions

PubMed Central

Leukel, Christian; Lundbye-Jensen, Jesper; Christensen, Mark Schram; Gollhofer, Albert; Nielsen, Jens Bo; Taube, Wolfgang

2012-01-01

Part of the sensory information is processed by our central nervous system without conscious perception. Subconscious processing has been shown to be capable of triggering motor reactions. In the present study, we asked the question whether visual information, which is not consciously perceived, could influence decision-making in a choice reaction task. Ten healthy subjects (28±5 years) executed two different experimental protocols. In the Motor reaction protocol, a visual target cue was shown on a computer screen. Depending on the displayed cue, subjects had to either complete a reaching movement (go-condition) or had to abort the movement (stop-condition). The cue was presented with different display durations (20–160 ms). In the second Verbalization protocol, subjects verbalized what they experienced on the screen. Again, the cue was presented with different display durations. This second protocol tested for conscious perception of the visual cue. The results of this study show that subjects achieved significantly more correct responses in the Motor reaction protocol than in the Verbalization protocol. This difference was only observed at the very short display durations of the visual cue. Since correct responses in the Verbalization protocol required conscious perception of the visual information, our findings imply that the subjects performed correct motor responses to visual cues, which they were not conscious about. It is therefore concluded that humans may reach decisions based on subconscious visual information in a choice reaction task. PMID:23049749

Catatonic variants, hyperthermic extrapyramidal reactions, and subtypes of neuroleptic malignant syndrome.

PubMed

Lee, Joseph W Y

2007-01-01

This case series study examines the hypothesis that neuroleptic malignant syndrome (NMS) is a heterogeneous condition including catatonic variants and non-catatonic pathological reactions to antipsychotics. Fourteen episodes of NMS were prospectively identified. Patients were examined for catatonia during the course of NMS. Close monitoring of catatonia episodes and suspected cases of evolving NMS for possible NMS development provided data on the pre-NMS clinical course. All NMS episodes received benzodiazepines. Episodes with catatonia diagnosed were compared with those without catatonia, noting their presentation, clinical course and responses to treatment. Concurrent catatonia was diagnosed in 9 episodes. In 6 of them antecedent catatonia progressed to NMS following antipsychotic exposure (NMS of antipsychotic-converted catatonia). In 3 episodes, a parkinsonian-catatonic syndrome with fever and autonomic abnormality developed in reaction to antipsychotics (NMS of antipsychotic-induced catatonia). Catatonia was not diagnosed in 5 during the longitudinal course of NMS. A severe extrapyramidal reaction to antipsychotics with associated delirium preceded all 5 episodes. Seven of the 9 NMS episodes with catatonia and none of the 5 without catatonia showed significant responses to benzodiazepines. The preliminary findings support the hypothesis that NMS is a heterogeneous condition including catatonic variants and non-catatonic hyperthermic extrapyramidal reactions to antipsychotics, differing in presentation, clinical course, and treatment responses.

Assignment of EC Numbers to Enzymatic Reactions with Reaction Difference Fingerprints

PubMed Central

Hu, Qian-Nan; Zhu, Hui; Li, Xiaobing; Zhang, Manman; Deng, Zhe; Yang, Xiaoyan; Deng, Zixin

2012-01-01

The EC numbers represent enzymes and enzyme genes (genomic information), but they are also utilized as identifiers of enzymatic reactions (chemical information). In the present work (ECAssigner), our newly proposed reaction difference fingerprints (RDF) are applied to assign EC numbers to enzymatic reactions. The fingerprints of reactant molecules minus the fingerprints of product molecules will generate reaction difference fingerprints, which are then used to calculate reaction Euclidean distance, a reaction similarity measurement, of two reactions. The EC number of the most similar training reaction will be assigned to an input reaction. For 5120 balanced enzymatic reactions, the RDF with a fingerprint length at 3 obtained at the sub-subclass, subclass, and main class level with cross-validation accuracies of 83.1%, 86.7%, and 92.6% respectively. Compared with three published methods, ECAssigner is the first fully automatic server for EC number assignment. The EC assignment system (ECAssigner) is freely available via: http://cadd.whu.edu.cn/ecassigner/. PMID:23285222

Conditions affecting the formation of chlorinated carbon compounds during carbochlorination

NASA Astrophysics Data System (ADS)

Landsberg, A.; Wilson, R. D.; Burns, W.

1988-06-01

The Bureau of Mines, United States Department of the Interior, has conducted an extensive study of the relationship between various metal oxide carbochlorination reactions and carbon compound byproducts. Experiments in which oxides of titanium, zirconium, and aluminum with graphite, charcoal, metallurgical coke, and pctroleum coke were chlorinated at 600° to 1000 °C produced 136 identified and quantified carbon byproduct compounds. The 20 most abundant of these compounds were correlated with reactants and reaction conditions. Experimental results support a proposed carbochlorination reaction with an initial chlorine-carbon step followed by a reaction between the resulting chlorine-carbon products and the metal oxide.

Synthesis of different-sized silver nanoparticles by simply varying reaction conditions with leaf extracts of Bauhinia variegata L.

PubMed

Kumar, V; Yadav, S K

2012-03-01

Green synthesis of nanoparticles is one of the crucial requirements in today's climate change scenario all over the world. In view of this, leaf extract (LE) of Bauhinia variegata L. possessing strong antidiabetic and antibacterial properties has been used to synthesise silver nanoparticles (SNP) in a controlled manner. Various-sized SNP (20-120 nm) were synthesised by varying incubation temperature, silver nitrate and LE concentrations. The rate of SNP synthesis and their size increased with increase in AgNO(3) concentration up to 4 mM. With increase in LE concentration, size and aggregation of SNP was increased. The size and aggregation of SNP were also increased at temperatures above and below 40°C. This has suggested that size and dispersion of SNP can be controlled by varying reaction components and conditions. Polarity-based fractionation of B. variegata LE has suggested that only water-soluble fraction is responsible for SNP synthesis. Fourier transform infrared spectroscopy analysis revealed the attachment of polyphenolic and carbohydrate moieties to SNP. The synthesised SNPs were found stable in double distilled water, BSA and phosphate buffer (pH 7.4). On the contrary, incubation of SNP with NaCl induced aggregation. This suggests the safe use of SNP for various in vivo applications.

On the implementation of a chain nuclear reaction of thermonuclear fusion on the basis of the p+{sup 11}B process

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

Belyaev, V. S.; Krainov, V. P., E-mail: vpkrainov@mail.ru; Zagreev, B. V.

2015-07-15

Various theoretical and experimental schemes for implementing a thermonuclear reactor on the basis of the p+{sup 11}B reaction are considered. They include beam collisions, fusion in degenerate plasmas, ignition upon plasma acceleration by ponderomotive forces, and the irradiation of a solid-state target from {sup 11}B with a proton beam under conditions of a Coulomb explosion of hydrogen microdrops. The possibility of employing ultra-short high-intensity laser pulses to initiate the p+{sup 11}B reaction under conditions far from thermodynamic equilibrium is discussed. This and some other weakly radioactive thermonuclear reactions are promising owing to their ecological cleanness—there are virtually no neutrons amongmore » fusion products. Nuclear reactions that follow the p+{sup 11}B reaction may generate high-energy protons, sustaining a chain reaction, and this is an advantage of the p+{sup 11}B option. The approach used also makes it possible to study nuclear reactions under conditions close to those in the early Universe or in the interior of stars.« less

Direct nuclear reaction experiments for stellar nucleosynthesis

NASA Astrophysics Data System (ADS)

Cherubini, S.

2017-09-01

During the last two decades indirect methods where proposed and used in many experiments in order to measure nuclear cross sections between charged particles at stellar energies. These are among the lowest to be measured in nuclear physics. One of these methods, the Trojan Horse method, is based on the Quasi-Free reaction mechanism and has proved to be particularly flexible and reliable. It allowed for the measurement of the cross sections of various reactions of astrophysical interest using stable beams. The use and reliability of indirect methods become even more important when reactions induced by Radioactive Ion Beams are considered, given the much lower intensity generally available for these beams. The first Trojan Horse measurement of a process involving the use of a Radioactive Ion Beam dealt with the ^{18} F(p, α ^{15} O process in Nova conditions. To obtain pieces of information on this process, in particular about its cross section at Nova energies, the Trojan Horse method was applied to the ^{18} F(d, α ^{15} O)n three body reaction. In order to establish the reliability of the Trojan Horse method approach, the Treiman-Yang criterion is an important test and it will be addressed briefly in this paper.

[Reactions to food].

PubMed

Halvorsen, R; Eggesb M; Botten, G

1995-12-10

Adverse reactions to food occur in about 1-2% of the population, but are reported more frequently by patients. Most reactions to food are not caused by allergy. IgE-mediated food reactions are well known and of major clinical significance owing to their potentially dangerous, even life-threatening character. Adverse reactions to food can also be caused by immunological mechanisms other than IgE-mediated reactions such as, enzyme deficiencies, active pharmacological substances in food and psychological mechanisms. Double-blind provocation is the only way to diagnose a positive reaction to a food item with some certainty. Regretably no objective measures for food reactions exist.

Chemical kinetic analysis of hydrogen-air ignition and reaction times

NASA Technical Reports Server (NTRS)

Rogers, R. C.; Schexnayder, C. J., Jr.