Kinetic Computation of Cyclization Reactions of Large Keto-Hydroperoxide Radicals in Low Temperature Combustion.

The cyclization reactions of keto-hydroperoxide (KHP) radicals leading to the formation of keto cyclic ethers and OH radicals play an important role in low temperature combustion for hydrocarbon fuels or oxygenated hydrocarbon fuels. However, due to the lack of kinetic data of cyclization reactions of KHP radicals, researchers often derive high-pressure-limit rate constants of cyclization reactions of KHP radicals from analogous cyclization reactions of hydroperoxyl alkyl radicals during construction of the combustion mechanism. This study aims to systematically investigate the kinetics of cyclization reactions of KHP radicals involving short-to-large-sized radicals. The studied reactions are divided into 7 reaction classes, according to the size of the cyclic transition state, the conjugative effect (whether KHP radicals are resonance-stabilized or not), and the position of the carbonyl group (whether the carbonyl group is inside or outside of the reaction center). The isodesmic reaction method, in conjunction with transition state theory, is utilized for each reaction class to compute the energy barriers and high-pressure-limit rate constants at the DFT level. The study revealed that energy barriers calculated at the DFT level with correction by the isodesmic reaction method are close to the results from the benchmark CCSD(T) method. To develop more accurate rate rules, these reaction classes are further divided into subclasses based on the relative site of the OOH group with the carbonyl group, the type of carbon atoms where the OOH group is located, and the type of carbon atoms where the radical site is located. For each subclass, high-pressure-limit rate rules are derived by averaging the rate constants of reactions in the subclass, and it is found that the maximum absolute deviation of the energy barrier and the ratio of the largest rate constant to the smallest rate constant among reactions in each subclass are within chemical accuracy limits, indicating acceptable use of the developed rate rules. A comparison of the rate constants for cyclization reactions of KHP radicals with the values of analogous cyclization reactions of hydroperoxyalkyl radicals as provided in reported mechanisms is made. Additionally, a comparison is drawn between our developed rate rules for subclasses of the cyclization reactions of KHP radicals and the rate rules for analogous subclasses of cyclization reactions of hydroperoxyl alkyl radicals. These comparisons demonstrate significant differences and highlight the necessity for improved rate rules for cyclization reactions of KHP radicals to enhance the automatically generated combustion mechanisms for hydrocarbon and oxygenated hydrocarbon fuels.

Investigating the kinetics of the intramolecular H-migration reaction class of methyl-ester peroxy radicals in low-temperature oxidation mechanisms of biodiesel.

Biodiesel is a promising, sustainable, and carbon-neutral fuel. However, studying its combustion mechanisms comprehensively, both theoretically and experimentally, presents challenges due to the complexity and size of its molecules. One significant obstacle in determining low-temperature oxidation mechanisms for biodiesel is the lack of kinetic parameters for the reaction class of intramolecular H-migration reactions of alkyl-ester peroxy radicals, labeled as R(CO)OR'-OO˙ (where the 'dot' represents the radical). Current biodiesel combustion mechanisms often estimate these parameters from the analogous reaction class of intramolecular H-migration reactions of alkyl peroxy radicals in alkane combustion mechanisms. However, such estimations are imprecise and neglect the unique characteristics of the ester group. This research aims to explore the kinetics of the reaction class of H-migration reactions of methyl-ester peroxy radicals. The reaction class is divided into 20 subclasses based on the newly formed cycle size of the transition state, the positions of the peroxy radical and the transferred H atom, and the types of carbons from which the H atom is transferred. Energy barriers for each subclass are calculated by using the CBS-QB3//M06-2X/6-311++G(d,p) method. High-pressure-limit and pressure-dependent rate constants ranging from 0.01 to 100 atm are determined using the transition state theory and Rice-Ramsberger-Kassel-Marcus/master-equation method, respectively. It is noted that the pressure-dependent rate constants calculated for each individual isomerization channel could bring some uncertainties while neglecting the interconnected pathways. A comprehensive comparison is made between our values of selected reactions and high-level calculated values of the corresponding reactions reported in the literature. The small deviation observed between these values indicates the accuracy and reliability of the energy barriers and rate constants calculated in this study. Additionally, our calculated high-pressure-limit rate constants are compared with the corresponding values in combustion mechanisms of esters, which were estimated based on analogous reactions of alkyl peroxy radicals. These comparative analyses shed light on the significant impact of the ester group on the kinetics, particularly when the ester group is involved in the reaction center. Finally, the high-pressure-limit rate rule and pressure-dependent rate rule for each subclass are derived by averaging the rate constants of reactions in each subclass. The accurate and reasonable rate rules for methyl-ester peroxy radicals developed in this study play a crucial role in enhancing our understanding of the low-temperature oxidation mechanisms of biodiesel.

Accurate Kinetics of Cyclization Reactions of the Large-Size Hydroperoxy Methyl-Ester Radicals Investigated by the Isodesmic Reaction Correction Method.

The cyclization reactions of hydroperoxymethylester radicals are pivotal in low-temperature methyl-ester combustion but limited experimental and theoretical kinetic data pose challenges. Prior research has drawn upon analogous hydroperoxy alkyl radical cyclization reactions to approximate rate constants and might inaccurately represent ester group-specific behavior. This study systematically investigates these kinetics, accounting for ester group effects and computational complexities in large molecular systems. The reactions are categorized into 11 classes based on cyclic transition state size and -OOH/radical positions. Energy barriers and high-pressure-limit rate constants are calculated using the isodesmic reaction correction method, validated, and applied to 24 subclasses based on carbon sites connected to -OOH and radical moieties. Subclass high-pressure-limit rate rules are derived through averaging rate constants. Analysis reveals uncertainties within acceptable chemical accuracy limits, validating the reaction classification and rate rules. We conduct comparative analyses with values from analogous alkyl reactions in established mechanisms while comparing our results with the high-pressure-limit rate rules for analogous alkane reactions. These comparisons reveal notable disparities, emphasizing the ester group's influence and necessitating tailored ester-specific rate rules. These findings hold promise for improving automatic reaction mechanism generation, particularly for large methyl esters.

Compact Combustion Mechanisms of Typical n-Alkanes Developed by the Minimized Reaction Network Method.

The existing combustion kinetic modeling method which aims at developing phenomenological combustion mechanisms characterized by multiple reactions confronts several challenges, including the conflicts between computing resources and mechanism scales during numerical simulation, etc. In order to address these issues, the minimized reaction network method for complex combustion system modeling based on the principle of simultaneous chemical equilibrium is proposed, which is aimed to develop combustion mechanisms with minimal reaction steps under a limited number of species. The concept of mechanism resolution is proposed in this method, and the reaction network with minimal reaction steps under a given mechanism resolution is constructed so that the scale of mechanisms is compressed greatly. Meanwhile, distinguishing from other mechanisms, the reversible form of elementary reactions is adopted and the classical two-parameter (A, Ea) Arrhenius equation fits the rate constants. Typical n-alkanes including n-butane, n-heptane, n-octane, n-decane, n-dodecane and n-hexadecane were taken as examples to indicate the development process of mechanisms and systematic kinetic validations were carried out. Results show that this method leads to very compact mechanisms with satisfactory accuracy, and it eliminates the process of mechanism reduction and is beneficial for mechanism optimization. This method and the derived kinetic mechanisms are hoped to contribute to combustion engineering applications.

Edaravone dexborneol promotes M2 microglia polarization against lipopolysaccharide-induced inflammation via suppressing TLR4/MyD88/NF-κB pathway.

Edaravone dexborneol (ED) is a novel neuroprotective compound that consists of two active ingredients, edaravone and ( +)-borneol in a 4:1 ratio, which has been shown the anti-inflammatory properties in animal models of ischemic stroke, cerebral hemorrhage, and autoimmune encephalomyelitis. However, the effect of ED on the polarization of microglia in neuroinflammation has not been elucidated. This study was to investigate the effects of ED on the polarization of microglia induced by lipopolysaccharide (LPS) and potential mechanisms. BV-2 microglial cells were incubated with ED (100, 200, and 400 µM) for 2 h, followed by lipopolysaccharide (LPS, 1 µg/ml) for 12 h. The researchers used the Griess method, western blot, immunocytochemistry, and subcellular fractionation to assess the effects and potential mechanisms of ED on neuroinflammatory reactions. The expression of ROS and the activities of antioxidant enzymes (SOD, GPx, and CAT) in LPS-induced BV-2 cells were also measured using the DCFH-DA fluorescent probe and colorimetric methods, respectively. It was observed that ED significantly declined the levels of TLR4/NF-κB pathway-associated proteins (TLR4, MyD88, p65, p-p65, IκBα, p-IκBα, IKKß, p-IKKß) and therefore inhibited LPS-induced production of NO, IL-1ß, and TNF-α. Moreover, ED markedly downregulated the M1 marker (iNOS) and upregulated the M2 marker (Arginase-1, Ym-1). In addition, ED also reduced ROS generation and enhanced GPx activity. ED induced the polarization of LPS-stimulated microglia from M1 to M2 against inflammation by negatively regulating the TLR4/MyD88/NF-κB signaling pathway. Additionally, ED performed antioxidative function by depleting the intracellular excessive ROS caused by LPS through the enhancement of the enzymatic activity of GPx. ED may be a potential agent to attenuate neuroinflammation via regulating the polarization of microglia.

ReaxFF molecular dynamics simulations of oxidation of toluene at high temperatures.

Aromatic hydrocarbon fuels, such as toluene, are important components in real jet fuels. In this work, reactive molecular dynamics (MD) simulations employing the ReaxFF reactive force field have been performed to study the high-temperature oxidation mechanisms of toluene at different temperatures and densities with equivalence ratios ranging from 0.5 to 2.0. From the ReaxFF MD simulations, we have found that the initiation consumption of toluene is mainly through three ways, (1) the hydrogen abstraction reactions by oxygen molecules or other small radicals to form the benzyl radical, (2) the cleavage of the C-H bond to form benzyl and hydrogen radicals, and (3) the cleavage of the C-C bond to form phenyl and methyl radicals. These basic reaction mechanisms are in good agreement with available chemical kinetic models. The temperatures and densities have composite effects on toluene oxidation; concerning the effect of the equivalence ratio, the oxidation reaction rate is found to decrease with the increasing of equivalence ratio. The analysis of the initiation reaction of toluene shows that the hydrogen abstraction reaction dominates the initial reaction stage at low equivalence ratio (0.5-1.0), while the contribution from the pyrolysis reaction increases significantly as the equivalence ratio increases to 2.0. The apparent activation energies, E(a), for combustion of toluene extracted from ReaxFF MD simulations are consistent with experimental results.

Effects of fuel additives on the thermal cracking of n-decane from reactive molecular dynamics.

Thermal cracking of n-decane and n-decane in the presence of several fuel additives are studied in order to improve the rate of thermal cracking by using reactive molecular dynamics (MD) simulations employing the ReaxFF reactive force field. From MD simulations, we find the initiation mechanisms of pyrolysis of n-decane are mainly through two pathways: (1) the cleavage of a C-C bond to form smaller hydrocarbon radicals, and (2) the dehydrogenation reaction to form an H radical and the corresponding decyl radical. Another pathway is the H-abstraction reactions by small radicals including H, CH(3), and C(2)H(5). The basic reaction mechanisms are in good agreement with existing chemical kinetic models of thermal decomposition of n-decane. Quantum mechanical calculations of reaction enthalpies demonstrate that the H-abstraction channel is easier compared with the direct C-C or C-H bond-breaking in n-decane. The thermal cracking of n-decane with several additives is further investigated. ReaxFF MD simulations lead to reasonable Arrhenius parameters compared with experimental results based on first-order kinetic analysis. The different chemical structures of the fuel additives greatly affect the apparent activation energy and pre-exponential factors. The presence of diethyl ether (DEE), methyl tert-butyl ether (MTBE), 1-nitropropane (NP), 3,6,9-triethyl-3,6,9-trimethyl-1,2,4,5,7,8-hexaoxonane (TEMPO), triethylamine (TEA), and diacetonediperodixe (DADP) exhibit remarkable promoting effect on the thermal cracking rates, compared with that of pure n-decane, in the following order: NP > TEMPO > DADP > DEE (∼MTBE) > TEA, which coincides with experimental results. These results demonstrate that reactive MD simulations can be used to screen for fuel additives and provide useful information for more comprehensive chemical kinetic model studies at the molecular level.

Multichannel photoinduced intramolecular electron-transfer excitations in a bis-naphthalimide spermine conjugate by time-dependent density functional theory.

Density functional theory was applied to the investigation of photoinduced electron transfer (ET) and the absorption spectrum for a bis-naphthalimide spermine conjugate. The multichannel feature of ET excitation in this system was focused on because four groups may act as electron donors and acceptors. The segment in this conjugate, N-(N-methylpropyl)-1,8-naphthalimide, which contains one donor and acceptor pair, was studied at first. Through theoretical calculation, the absorption band at 340 nm was assigned to the pi-->pi* transition. For the whole system involving four chromophores, this work suggested three types of ET. From the theoretical investigation, the naphthalimide radical anion turned out to be formed via intramolecular ET between the two terminal naphthalimide groups, rather than via the electron transfer between the dialkylamine moiety and the naphthalimide one. Furthermore, the electronic coupling matrix elements according to the generalized Mulliken-Hush theory were estimated and the detailed analyses showed that the strongest absorption was due to the local excitation of the naphthalimide chromophore.