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The relative rates of C-C and C-H β-scission reactions of isobutyl radicals (2-methylprop-1-yl, CH) were investigated with shock tube experiments at temperatures of (950 to 1250) K and pressures of (200 to 400) kPa. We produced isobutyl radicals from the decomposition of dilute mixtures of isopentylbenzene and observed the stable decomposition products, propene and isobutene. These alkenes are characteristic of C-C and C-H bond scission, respectively. Propene was the main product, approximately 30 times more abundant than isobutene, indicating that C-C β-scission is the primary pathway. Uncertainty in the ratio of [isobutene]/[propene] from isobutyl decomposition is mainly due to a small amount of side chemistry, which we account for using a kinetics model based on JetSurF 2.0. Our data are well-described after adding chemistry specific to our system and adjusting some rate constants. We compare our data to other commonly used kinetics models: JetSurF 2.0, AramcoMech 2.0, and multiple models from Lawrence Livermore National Laboratory (LLNL). With the kinetics model, we have determined an upper limit of 3.0% on the branching fraction for C-H β-scission in the isobutyl radical for the temperatures and pressures of our experiments. While this agrees with previous high quality experimental results, many combustion kinetics models assume C-H branching values above this upper limit, possibly leading to large systematic inaccuracies in model predictions. Some kinetics models additionally assume contributions from 1,2-H shift reactions-which for isobutyl would produce the same products as C-H β-scission-and our upper limit includes possible involvement of such reactions. We suggest kinetics models should be updated to better reflect current experimental measurements.
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http://dx.doi.org/10.1021/acs.jpca.8b01194 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Shenzhen institute of advanced technology Chinese Academy of Sciences, Functional Thin Films Research Centre, 1068 Xueyuan Avenue, Shenzhen University Town, 518000, SHENZHEN, CHINA.
Organics electrode materials offer multi-electron reactivity, flexible structures, and redox reversibility, but encounter poor conductivity and durability in electrolytes. To overcome above barriers, we propose a dual elongation strategy of π-conjugated motifs with active sites, involving extended carbazole and electropolymerized crosslinked polymer, which enhances electronic conductivity by the electronic delocalization of electron-withdrawing conjugated groups, boosts theoretical capacity by increasing redox-active site density, and endows robust electrochemical stability attributed to crosslinked organic structures. As a proof-of-concept, 5,11-dihydridoindolo[3,2-b]carbazole (DHIC) is selected as the model cathode material for a dual-ion battery, with elongated carbazole groups functioning both as redox-active centers and polymerization anchors.
View Article and Find Full Text PDFBackground: TPM3 (tropomyosin 3) is an actin-binding protein in vascular smooth muscle cells, where posttranslational modifications critically regulate its actin affinity, influencing cardiovascular function. Emerging evidence suggests that Khib (2-hydroxyisobutyrylation) plays a significant role in the cardiovascular system. Histone deacetylase 3 (HDAC3) serves as an "eraser" of Khib marks.
View Article and Find Full Text PDFACS Nano
December 2024
Department of Physics, Syracuse University, 201 Physics Building, Syracuse, New York 13244-1130, United States.
Two or more protein ligands may compete against each other to interact transiently with a protein receptor. While this is a ubiquitous phenomenon in cell signaling, existing technologies cannot identify its kinetic complexity because specific subpopulations of binding events of different ligands are hidden in the averaging process in an ensemble. In addition, the limited time resolution of prevailing methods makes detecting and discriminating binding events among diverse interacting partners challenging.
View Article and Find Full Text PDFChaos
December 2024
Centre for Mathematical Biology and Ecology, Department of Mathematics, Jadavpur University, Kolkata 700032, India.
This study expands traditional reaction-diffusion models by incorporating hyperbolic dynamics to explore the effects of inertial delays on pattern formation. The kinetic system considers a harvested predator-prey model where predator and prey populations gather in herds. Diffusion and inertial effects are subsequently introduced.
View Article and Find Full Text PDFChem Commun (Camb)
December 2024
School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300401, China.
In this study, five catalysts with Pd particle sizes ranging from single atoms to nanoclusters and nanoparticles were synthesized by controlling the Pd loading amount and preparation methods, and applied in the hydrogenation of FDCA to THFDCA. Furthermore, kinetic models were established. Notably, the nanocluster catalyst demonstrated relatively high hydrogenation activity.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!