scholarly journals CHEMICAL CONVERSIONS OF REDUCED CARBON COMPOUNDS AND NITROGEN OXIDES IN THE CRAMPED AERODYNAMIC CONDITIONS OF THE URBAN ATMOSPHERE

2021 ◽  
Vol 57 ◽  
pp. 111-117
Author(s):  
Vadim A. Zaytsev ◽  
Keyword(s):  
Nitrogen Oxides ◽  
Reaction Rates ◽  
Urban Atmosphere ◽  
Chemical Transformations ◽  
Stiff System ◽  
Rosenbrock Method ◽  
Wide Range ◽  
Carbon Compounds ◽  
High Concentrations ◽  
Kinetics Of

The kinetics of chemical transformations of the most significant pollutants in the cramped aerodynamic conditions of the urban atmosphere is considered, i.e. in the gaps between rows of wide buildings with significant height. High concentrations created in those areas lead to sufficiently high values of reaction rates. The process is described by a stiff system of differential equations, the solution of which is performed by Rosenbrock method. The effect of reduced carbon compounds and nitrogen oxides in a wide range of their concentrations on the rate of formation of a highly toxic secondary pollutant is investigated. In the course of numerical experiments, conditions are determined that correspond to its maximum value. In that case, the transfer of substances from the reaction zone does not have time to occur.

scholarly journals Atmospheric chemistry and physics in the atmosphere of a developed megacity (London): an overview of the REPARTEE experiment and its conclusions

2012 ◽  
Vol 12 (6) ◽  
pp. 3065-3114 ◽  
Author(s):  
R. M. Harrison ◽  
M. Dall'Osto ◽  
D. C. S. Beddows ◽  
A. J. Thorpe ◽  
W. J. Bloss ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Gas Phase ◽  
Atmospheric Chemistry ◽  
Urban Atmosphere ◽  
Trace Gas ◽  
Chemical Components ◽  
Chemical Transformations ◽  
Specific Chemical ◽  
Gas Dispersion ◽  
Wide Range

Abstract. The REgents PARk and Tower Environmental Experiment (REPARTEE) comprised two campaigns in London in October 2006 and October/November 2007. The experiment design involved measurements at a heavily trafficked roadside site, two urban background sites and an elevated site at 160–190 m above ground on the BT Tower, supplemented in the second campaign by Doppler lidar measurements of atmospheric vertical structure. A wide range of measurements of airborne particle physical metrics and chemical composition were made as well as measurements of a considerable range of gas phase species and the fluxes of both particulate and gas phase substances. Significant findings include (a) demonstration of the evaporation of traffic-generated nanoparticles during both horizontal and vertical atmospheric transport; (b) generation of a large base of information on the fluxes of nanoparticles, accumulation mode particles and specific chemical components of the aerosol and a range of gas phase species, as well as the elucidation of key processes and comparison with emissions inventories; (c) quantification of vertical gradients in selected aerosol and trace gas species which has demonstrated the important role of regional transport in influencing concentrations of sulphate, nitrate and secondary organic compounds within the atmosphere of London; (d) generation of new data on the atmospheric structure and turbulence above London, including the estimation of mixed layer depths; (e) provision of new data on trace gas dispersion in the urban atmosphere through the release of purposeful tracers; (f) the determination of spatial differences in aerosol particle size distributions and their interpretation in terms of sources and physico-chemical transformations; (g) studies of the nocturnal oxidation of nitrogen oxides and of the diurnal behaviour of nitrate aerosol in the urban atmosphere, and (h) new information on the chemical composition and source apportionment of particulate matter size fractions in the atmosphere of London derived both from bulk chemical analysis and aerosol mass spectrometry with two instrument types.

scholarly journals Kinetics of Decomposition Reactions of Acetic Acid Using DFT Approach

2018 ◽  
Vol 12 (1) ◽  
pp. 14-23 ◽  
Author(s):  
Anand Mohan Verma ◽  
Nanda Kishore
Keyword(s):  
Acetic Acid ◽  
Reaction Pathway ◽  
Reaction Rates ◽  
Basis Set ◽  
Ground State Structure ◽  
Decomposition Reactions ◽  
Dehydration Reactions ◽  
Wide Range ◽  
Bio Oil ◽  
Kinetics Of

Object: Excessive amount of oxygen content in unprocessed bio-oil deteriorates the quality of bio-oil which cannot be used in transportation vehicles without upgrading. Acetic acid (CH3COOH) is a vital component of ‘acids’ catalogue of unprocessed bio-oil produced from thermochemical conversions of most of biomass feedstocks such as switchgrass, alfalfa, etc. In this study, the decomposition reactions of acetic acid are carried out by two reaction pathways, i.e., decarboxylation and dehydration reactions. In addition, the reaction rates of decomposition are analysed in a wide range of temperatures, i.e., 298-900 K and at atmospheric pressure. Method: All quantum chemical calculations are performed in the gas phase using two DFT functionals, B3LYP and M06-2X, with 6-31g(d) basis set. The dehydration reaction of acetic acid proceeds directly from ground state structure of acetic acid, whereas, decarboxylation reaction forms an unstable intermediate of acetic acid to initiate the proton migration. Barrier height and kinetics study for both reactions and theories are different and illustrated in the reaction pathway and rate profiles, respectively. Furthermore, both levels of theories offer similar structural configurations but they differ slightly in energetics. Conclusion: The reaction kinetics of both reactions is linearly fitted and the Arrhenius equations corresponding to each decomposition mechanism are generated by fitting the data from line equation.

scholarly journals Platinum catalyzed hydrodeoxygenation of guaiacol in illumination of cresol production: a density functional theory study

2017 ◽  
Vol 4 (11) ◽  
pp. 170650 ◽  
Author(s):  
Anand Mohan Verma ◽  
Nanda Kishore
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Reaction Rates ◽  
Transportation Fuel ◽  
Phenolic Fraction ◽  
Functional Theory ◽  
Heating Value ◽  
Wide Range ◽  
Bio Oil ◽  
Kinetics Of

The unprocessed bio-oil obtained by the pyrolysis of lignocellulosic biomass comprises hundreds of oxy-components which vitiate its quality in terms of low heating value, low stability, low pH, etc. Therefore, it has to be upgraded prior to its use as transportation fuel. In this work, guaiacol, a promising compound of the phenolic fraction of unprocessed bio-oil, is considered as a model component for studying its hydrodeoxygenation over a Pt 3 catalyst cluster. The production of catechol, 3-methylcatechol, m -cresol and o -cresol from guaiacol over a Pt 3 cluster is numerically investigated using density functional theory. Further, the kinetic parameters are obtained over a wide range of temperature, i.e. 473–673 K at an interval of 50 K. Briefly, results indicate that O─H and C─H bond scissions determine the reaction rates of ‘guaiacol to catechol’ and ‘catechol to 3-methylcatechol’ reactions with activation energies of 30.32 and 41.3 kcal mol −1 , respectively. On the other hand, C─O bond scissions determine the rates of 3-methylcatechol to m - and o -cresol production reactions, respectively. The kinetics of all reactions indicate that ln k versus 1/ T plots are linear over the entire range of temperature considered herein.

scholarly journals Atmospheric chemistry and physics in the atmosphere of a developed megacity (London): an overview of the REPARTEE experiment and its conclusions

2011 ◽  
Vol 11 (11) ◽  
pp. 30145-30271 ◽  
Author(s):  
R. M. Harrison ◽  
M. Dall'Osto ◽  
D. C. S. Beddows ◽  
A. J. Thorpe ◽  
W. J. Bloss ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Gas Phase ◽  
Atmospheric Chemistry ◽  
Urban Atmosphere ◽  
Trace Gas ◽  
Chemical Components ◽  
Chemical Transformations ◽  
Specific Chemical ◽  
Gas Dispersion ◽  
Wide Range

Abstract. The Regents Park and Tower Environmental Experiment (REPARTEE) comprised two campaigns in London in October 2006 and October/November 2007. The experiment design involved measurements at a heavily trafficked roadside site, two urban background sites and an elevated site at 160–190 m above ground on the BT Tower, supplemented in the second campaign by Doppler lidar measurements of atmospheric vertical structure. A wide range of measurements of airborne particle physical metrics and chemical composition were made as well as measurements of a considerable range of gas phase species and the fluxes of both particulate and gas phase substances. Significant findings include (a) demonstration of the evaporation of traffic-generated nanoparticles during both horizontal and vertical atmospheric transport; (b) generation of a large base of information on the fluxes of nanoparticles, accumulation mode particles and specific chemical components of the aerosol and a range of gas phase species, as well as the elucidation of key processes and comparison with emissions inventories; (c) quantification of vertical gradients in selected aerosol and trace gas species which has demonstrated the important role of regional transport in influencing concentrations of sulphate, nitrate and secondary organic compounds within the atmosphere of London; (d) generation of new data on the atmospheric structure and turbulence above London, including the estimation of mixed layer depths; (e) provision of new data on trace gas dispersion in the urban atmosphere through the release of purposeful tracers; (f) the determination of spatial differences in aerosol particle size distributions and their interpretation in terms of sources and physico-chemical transformations; (g) studies of the nocturnal oxidation of nitrogen oxides and of the diurnal behaviour of nitrate aerosol in the urban atmosphere, and (h) new information on the chemical composition and source apportionment of particulate matter size fractions in the atmosphere of London derived both from bulk chemical analysis and aerosol mass spectrometry with two instrument types.

scholarly journals A general in vitro assay to study enzymatic activities of the ubiquitin system

2019 ◽  
Author(s):  
Yukun Zuo ◽  
Boon Keat Chong ◽  
Kun Jiang ◽  
Daniel Finley ◽  
David Klenerman ◽  
...  
Keyword(s):  
Reaction Rates ◽  
Vitro Assay ◽  
Protein Ubiquitination ◽  
Ubiquitination Assay ◽  
Ubiquitin System ◽  
Wide Range ◽  
Machine Learning Approach ◽  
Fret Efficiency ◽  
Kinetics Of

AbstractThe ubiquitin (Ub) system regulates a wide range of cellular signaling pathways. Several hundred E1, E2 and E3 enzymes are together responsible for protein ubiquitination, thereby controlling cellular activities. Due to the numerous enzymes and processes involved, studies on ubiquitination activities have been challenging. We here report a novel FRET-based assay to study the in vitro kinetics of ubiquitination. FRET is established between binding of fluorophore-labeled Ub to eGFP-tagged ZnUBP, a domain that exclusively binds unconjugated Ub. We name this assay the Free Ub Sensor System (FUSS). Using Uba1, UbcH5 and CHIP as model E1, E2 and E3 enzymes, respectively, we demonstrate that ubiquitination results in decreasing FRET efficiency, from which reaction rates can be determined. Further treatment with USP21, a deubiquitinase, leads to increased FRET efficiency, confirming the reversibility of the assay. We subsequently use this assay to show that increasing the concentration of CHIP or UbcH5 but not Uba1 enhances ubiquitination rates, and develop a novel machine learning approach to model ubiquitination. The overall ubiquitination activity is also increased upon incubation with tau, a substrate of CHIP. Our data together demonstrate the versatile applications of a novel ubiquitination assay that does not require labeling of E1, E2, E3 or substrates, and is thus likely compatible with any E1-E2-E3 combinations.

Scintigraphic studies in rats. Kinetics of insulin analogues covering wide range of receptor affinities

Diabetes ◽  
1991 ◽  
Vol 40 (5) ◽  
pp. 628-632 ◽  
Author(s):  
I. Jensen ◽  
V. Kruse ◽  
U. D. Larsen
Keyword(s):  
Insulin Analogues ◽  
Wide Range ◽  
Kinetics Of

Strongly Coupled Redox-Linked Conformational Switching at the Active Site of the Non-Heme Iron-Dependent Dioxygenase, TauD

2019 ◽  
Author(s):  
Christopher John ◽  
Greg M. Swain ◽  
Robert P. Hausinger ◽  
Denis A. Proshlyakov
Keyword(s):  
Active Site ◽  
Structural Model ◽  
Heme Iron ◽  
Chemical Transformations ◽  
Experimental Conditions ◽  
Strongly Coupled ◽  
Non Heme Iron ◽  
Reversible Redox ◽  
Wide Range ◽  
Complex Structural

2-Oxoglutarate (2OG)-dependent dioxygenases catalyze C-H activation while performing a wide range of chemical transformations. In contrast to their heme analogues, non-heme iron centers afford greater structural flexibility with important implications for their diverse catalytic mechanisms. We characterize an <i>in situ</i> structural model of the putative transient ferric intermediate of 2OG:taurine dioxygenase (TauD) by using a combination of spectroelectrochemical and semi-empirical computational methods, demonstrating that the Fe (III/II) transition involves a substantial, fully reversible, redox-linked conformational change at the active site. This rearrangement alters the apparent redox potential of the active site between -127 mV for reduction of the ferric state and 171 mV for oxidation of the ferrous state of the 2OG-Fe-TauD complex. Structural perturbations exhibit limited sensitivity to mediator concentrations and potential pulse duration. Similar changes were observed in the Fe-TauD and taurine-2OG-Fe-TauD complexes, thus attributing the reorganization to the protein moiety rather than the cosubstrates. Redox difference infrared spectra indicate a reorganization of the protein backbone in addition to the involvement of carboxylate and histidine ligands. Quantitative modeling of the transient redox response using two alternative reaction schemes across a variety of experimental conditions strongly supports the proposal for intrinsic protein reorganization as the origin of the experimental observations.

Kinetics of esterification of monoisopropylphenols with phosphoryl trichloride

1989 ◽  
Vol 54 (5) ◽  
pp. 1311-1317
Author(s):  
Miroslav Magura ◽  
Ján Vojtko ◽  
Ján Ilavský
Keyword(s):  
Liquid Phase ◽  
Rate Constants ◽  
Reaction Rates ◽  
Activation Energies ◽  
The Individual ◽  
Kinetics Of

The kinetics of liquid-phase isothermal esterification of POCl3 with 2-isopropylphenol and 4-isopropylphenol have been studied within the temperature intervals of 110 to 130 and 90 to 110 °C, respectively. The rate constants and activation energies of the individual steps of this three-step reaction have been calculated from the values measured. The reaction rates of the two isomers markedly differ: at 110 °C 4-isopropylphenol reacts faster by the factors of about 7 and 20 for k1 and k3, respectively. This finding can be utilized in preparation of mixed triaryl phosphates, since the alkylation mixture after reaction of phenol with propene contains an excess of 2-isopropylphenol over 4-isopropylphenol.

An Investigation on the Performance of an Oxidation Catalyst Using Two-dimensional Simulation with Detailed Reaction Mechanism

2020 ◽  
Vol 0 (0) ◽  
Author(s):  
Sreeharsh Nair ◽  
Mayank Mittal
Keyword(s):  
Single Channel ◽  
Catalytic Converter ◽  
Oxidation Catalyst ◽  
Low Temperature Combustion ◽  
Wide Range ◽  
Detailed Reaction Mechanism ◽  
Temperature Combustion ◽  
High Concentrations ◽  
Dimensional Simulation ◽  
Surface Reaction Kinetics

AbstractThe advent of stricter emission standards has increased the importance of aftertreatment devices and the role of numerical simulations in the evolution of better catalytic converters in order to satisfy these emission regulations. In this paper, a 2-D numerical simulation of a single channel of the monolith catalytic converter is presented by using detailed surface reaction kinetics aiming to investigate the chemical behaviour inside the converter. The model has been developed to study the conversion of carbon monoxide (CO) in the presence of propene (C3H6) for low-temperature combustion (LTC) engine application. The inhibition effect of C3H6 over a wide range of CO inlet concentrations is investigated. Considering both low and high levels of CO concentration at the inlet, the 2-D model predicted better results than their corresponding 1-D counterparts when compared with the experimental data from literature. It was also observed that C3H6 inhibition at high temperatures was significant, particularly for high concentrations of CO compared to low concentrations of CO at the inlet.

Application of the EYTEX™ System to the Evaluation of Cosmetic Products and their Ingredients

1992 ◽  
Vol 20 (1) ◽  
pp. 146-163
Author(s):  
Francis H. Kruszewski ◽  
Laura H. Hearn ◽  
Kyle T. Smith ◽  
Janice J. Teal ◽  
Virginia C. Gordon ◽  
...  
Keyword(s):  
Double Blind ◽  
Eye Irritation ◽  
Ocular Irritation ◽  
Rabbit Eye ◽  
Wide Range ◽  
High Concentrations ◽  
Alkaline Membrane ◽  
Positive Agreement

465 cosmetic product formulations and raw ingredients were evaluated with the EYTEX™ system to determine the potential of this in vitro alternative for identifying eye irritation potential. The EYTEX™ system is a non-animal, biochemical procedure developed by Ropak Laboratories, Irvine, CA, that was designed to approximate the Draize rabbit eye irritation assay for the evaluation of ocular irritation. Avon Products Inc. provided all the test samples, which included over 30 different product types and represented a wide range of eye irritancy. All the EYTEX™ protocols available at the time of this study were used. Samples were evaluated double-blind with both the membrane partition assay (MPA) and the rapid membrane assay (RMA). When appropriate, the standard assay (STD) and the alkaline membrane assay (AMA) were used, as well as specific, documented protocol modifications. EYTEX™ results were correlated with rabbit eye irritation data which was obtained from the historical records of Avon Products Inc. A positive agreement of EYTEX™ results with the in vivo assay was demonstrated by an overall concordance of 80%. The assay error was 20%, of which 18% was due to an overestimation of sample irritancy (false positives) and 2% was attributed to underestimation (false negatives). Overestimation error in this study was due in part to the inability of the protocols to accurately classify test samples with very low irritation potential. Underestimation of sample irritancy was generally associated with ethoxylated materials and high concentrations of specific types of surfactants. 100% sensitivity and 85% predictability were described by the data, indicating the efficiency of EYTEX™ in identifying known irritants. A specificity rate of 39% showed the EYTEX™ assay to be weak in discerning non-irritants. However, the EYTEX™ protocols used in this study were not designed to identify non-irritants. A compatibility rate of 99% proved the effectiveness of the EYTEX™ assay in accommodating a diversity of product types. The EYTEX™ system protocols, when used appropriately, can provide a conservative means of assessing the irritant potential of most cosmetic formulations and their ingredients.

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