Radical Decomposition Research Articles

Experimental and molecular dynamics study on combustion characteristics of non-stick coal

To investigate the combustion characteristics of non-stick coal and the formation patterns of main combustion products and radicals, this study initially conducted a TG-DSC experiment of non-stick coal. Subsequently, non-stick coal was characterized and analyzed using XPS and 13C NMR experiments, and a molecular model with the formula C208H199O23N3S was constructed. Subsequently, the ReaxFF MD method was employed to simulate the combustion molecular dynamics of the non-stick coal periodic mixing model under varying oxygen content and temperature conditions. The analysis focused on elucidating the formation patterns of free and primary products during combustion. Experimental findings indicate that the combustion of non-stick coal progresses through stages, including water evaporation and desorption (30–145.65 °C), dynamic equilibrium (145.65–181.76 °C), oxygen weight gain (181.76–263.56 °C), thermal decomposition (263.56–379.14 °C), combustion (379.14–562.04 °C) and burnout (562.04–800 °C). The ignition temperature of non-stick coal was determined to be 379.14 °C. The simulation results indicate that an increase in temperature and oxygen content further enhances the relatively stable peak production of CO2. The peak increase of CO production is weaker than that of CO2. The rise in temperature also promotes the formation of H2O, while the increase in oxygen content initially enhances and subsequently inhibits the peak production of H2O. H radicals, O radicals, and OH radicals are primarily generated through the decomposition reactions of small molecular compounds or other free radicals. Free radical polymerization and the decomposition of small molecular compounds represent the primary pathways for the formation of CO, CO2, and H2O.

Ether and ester formation from peroxy radical recombination: a qualitative reaction channel analysis

Abstract. The least volatile organic compounds participating in atmospheric new-particle formation are very likely accretion products from self- and cross-reactions of peroxy radicals (RO2). It has long been assumed that the only possible accretion product channel in this reaction is that forming a peroxide (RO2+RO2→ROOR+O2), but it has recently been discovered that a rapid alkoxy radical (RO) decomposition may precede the accretion step of the mechanism, forming slightly fragmented but more stable ether (ROR) or ester (RC′(O)OR) accretion products. In this work, the atmospheric implications of this new reaction channel have been explored further by using a modified version of the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) software to generate a large amount of representative RO2 + RO2 reactive pairs formed from the oxidation of typical primary hydrocarbons and by applying structure–activity relationships (SARs) to predict the potential accretion products. These data are analysed in terms of the formation of low-volatility products, and new discoveries are presented on what types of RO2 are especially efficient (and which are surprisingly inefficient) at forming accretion products. These findings are discussed in terms of the atmospheric relevance of these new RO2 + RO2 reaction channels. As the generation of these data rests on several simplifications and assumptions, many open questions worthy of later studies are also raised.

Study of the potential energy surface of reactions in a system containing <i>i</i>-propyl and <i>n</i>-propyl radicals

The energy pathways of possible decomposition and isomerization reactions of iso-propyl (i-C3H7) and n-propyl (n-C3H7) radicals have been studied by computational methods of quantum chemistry. B3LYP, M062X, MP2, and CBS-QB3 methods are used to localize stationary points on the potential energy surface of a system containing propyl radicals. A number of intermediate compounds formed during the isomerization and decomposition of propyl radicals have been identified, and information has been obtained on their structure and thermochemical parameters. Based on the results of the research, a diagram of the energy levels of the system under consideration was constructed.

Treatment of high-concentration semi-coke wastewater by phenolic condensation and persulfate oxidation

In this study, the combined process of phenolic condensation-persulfate(PS) advanced oxidation was adopted to treat semi-coking wastewater. Using the phenolic condensation method as a pretreatment unit to remove phenolic substances for the preparation of phenol-formaldehyde resins, and using an aerated/PS/pyrite oxidation system as a deep treatment unit to remove chemical oxygen demand (COD) and ammonia nitrogen (NH3-N) from the wastewater. Analysis and characterization of phenol-formaldehyde resin, organic compounds in wastewater, and pyrite using FT-IR, TG-DTG, GC-MS, and XPS techniques. The results showed that under the conditions of adding 1.8vt % formaldehyde, pH 10.5, reaction temperature 95 ℃ and reaction time 3 h, the removal rates of volatile phenol, COD and NH3-N in semi-coke wastewater were 97.54 %, 41.14 % and 56.50 %, and the yield of phenolic resin was 6.62 g/L. Subsequently, treated with an aerated/PS/pyrite system, the PS concentration 0.4 mol/L, the pyrite dosage 15 g/L, the pH 3, the temperature 65 ℃, and the aeration 3 h, the removal rates of COD and NH3-N are 99.20 % and 86.80 %. In the phenolic condensation process, phenolic substances in semi-coke wastewater generate phenoxy anions under the influence of OH-, which undergo addition reactions with formaldehyde to produce hydroxymethyl phenol. Hydroxymethyl phenol further undergoes condensation reactions with other phenolic substances and itself to form phenolic resin, while amide compounds are generated through reactions between ammonia nitrogen and carboxylic acid substances. In the aeration/PS/pyrite system, Fe2+ released from pyrite oxidation activates PS to produce SO4•− and O2•−. The contribution of free radical oxidation and decomposition of pollutants such as phenols, amides, and NH3-N in wastewater is 84.60 %. Specifically, SO4•− oxidation contributes 61.54 %, while O2•− accounts for 22.21 %. Amide compounds and phenolic substances in the wastewater are oxidized, leading to ring opening and chain scission, resulting in the formation of alkane compounds.

Kinetic analysis on the hydrogen cyanide formation in the premixed methane/ammonia flame

Hydrogen cyanide (HCN) is a highly toxic trace emission that may be generated during ammonia (NH3) blended hydrocarbon combustion. In this study, a new kinetic model was developed and validated to predict HCN formation in NH3-blended combustion. Key rate coefficients for nitrogen-substituted hydrocarbon species were critically reevaluated. Using a one-dimensional freely propagating flame model, the formation of HCN in laminar premixed CH4/NH3/air flames was systematically analyzed under various conditions. Results indicate that HCN emission increases with increasing equivalence ratio (ϕ) and non-monotonically changes with NH3 blending ratio (α). Under lean conditions, HCN is primarily formed from the decomposition of imine radicals and oxidized by O/OH inside the flame front. While under rich conditions, the HCN oxidation takes place in the post-flame region, making the emissions at the outlet highly dependent on the reaction residential time. Consequently, attention should be paid to HCN emissions under high NH3 blending fraction (α > 50 %), and ultra-rich conditions (ϕ > 1.2) at normal temperature and pressure. The peak emission of HCN occurred at α = 0.7 and ϕ = 1.45, reaching a lethal concentration (310 ppm) in 1D premixed flame. Complex CHi and NHi interaction reactions are exhibited in the formation of HCN. The overall formation route can be divided into methylamine oxidation routes and radical combinations routes, and the former is dominant under all conditions. Independently increasing temperature or pressure will reduce the HCN emission due to the increased post-oxidation of HCN and diminished reaction characteristic time, respectively. More complicated changes in HCN were shown when temperature and pressure were increased at the same time. However, emissions will fall to a negligible level when temperature and pressure exceed 600 K and 2 atm, suggesting minimal concern for HCN emissions in CH4/NH3 combustion under elevated pressure and temperature conditions.

Theoretical and experimental study on the pyrolysis of N-methylpyrrolidone

As a widely used organic solvent, N-methylpyrrolidone (NMP) may suffer thermal decomposition during large-scale industrial usage. The complex potential energy surface and corresponding pressure-dependent rate coefficients of NMP and NMP radicals were obtained at a high level of theory. The intermediates and products of NMP pyrolysis within 900–1200 K were identified and measured by synchrotron vacuum ultraviolet photoionization mass spectrometry. Theoretical calculations show that the Keto-enol tautomerization and direct ring-opening channel yielding C2H4, CO, and CH3NCH2 exhibit the highest rate coefficient among NMP unimolecular reactions at low and high temperatures, respectively. However, the fuel decomposition process cannot be exclusively dominated by single low-barrier channel. The ring-opening reaction forming imino aldehyde radical and following decarbonylation reactions are favored channels during the NMP radical decomposition, while the formation of the dihydropyrrolidone via H or CH3 loss competes with them at higher temperatures. Various smaller heterocycle radicals can be produced and act as intermediates for the multi-step isomerization of the ring-opening products with a relatively low energy barrier, changing the position of the functional group and radical site. A variety of nitrogenous and oxygenated species were observed in the experiment, such as ketene, methyl isocyanate, pyrrole, benzene, and different kinds of imines. Among them, C2H4, HCN, and CO are the major products for NMP decomposition. Potential reaction pathways from NMP to the major experimentally observed products were inferred based on the calculated results and existing knowledge on the pyrolysis of nitrogenous and oxygenated compounds. These results shed light on the complex C/H/O/N reaction system. The calculated rate coefficients and extensive mole fractions data could provide good support for the modeling of a detailed reaction mechanism in the future.

Reassessment of the High-Temperature Oxidation of Di Ethyl Ether through Ab Initio Calculations.

Recent investigations of diethyl ether (DEE) high-temperature pyrolysis and fuel-rich oxidation have highlighted the failure of existing kinetic models to describe experimental CO production. The DEE high-temperature pyrolysis and oxidation chemistry is thus investigated through ab initio calculations. Geometries, frequencies, and hindered-rotor potentials of reactants, products, and transition states of key reactions (fuel decomposition radical decomposition and H-abstraction reactions) are calculated with the B2PLYP-D3/def2-TZVPD method, whereas final energies are refined using CCSD(T)/aug-cc-pV(D,T)Z. Temperature- and pressure-dependent rate constants are then derived from either canonical transition state theory (CTST) or ME/RRKM analysis with the inclusion of tunneling effect and hindered-rotor corrections and compared to experimental measurements when available as well as to previously suggested values. This new information is then merged with a C0-C3 core chemistry model and a low-temperature chemistry DEE subset from the literature to propose a new kinetic model for the combustion of DEE. This model is tested successfully against a large database related to the high-temperature oxidation and pyrolysis chemistry of DEE, including ignition delay times, shock tube speciation data, time-resolved CO profiles, laminar flame speeds, flame structures, and jet-stirred reactor data.

Radical decomposition of hydrogen peroxide catalyzed by iodide for degradation of organic dyes

The decomposition of hydrogen peroxide into hydroxyl radical, a powerful oxidizing agent, has aroused the interest of the scientific community due to the numerous possible applications, mainly in the treatment of effluents. In this work, the potential of using iodide ions as precursors of the hydroxyl radical was evaluated. Iodide, in addition to being theoretically viable, simultaneously leads to the production of molecular iodine, which also has an oxidizing characteristic, and can contribute to the efficiency of the process. The results demonstrated that iodide ions act by promoting the radical decomposition of H2O2 and that the process is dependent on the pH of the reaction medium, with the generation of radical hydroxyl only manifesting itself at pH 2.5 and 3.0. The removal results proved that the anionic or cationic nature of the dye interferes with the reaction mechanism. For methylene blue, a cationic dye, a small portion of TOC was removed by oxidation (7.9 to 20.6%) and the remainder occurred by adsorption (79.4 and 92.1%). The interaction of methylene blue with the surface of molecular iodine prevents its contact with the iodide ions present in the reaction medium, allowing it to remain in a solid state in solution and act as an adsorbent, contributing to better efficiency. For the tartrazine yellow dye, an anionic dye, there was no formation of solid iodine, indicating the absence of an adsorptive process, with the oxidation mechanism, showing removal of 11.3 to 18.9%, similar to the results found for the removal of blue. methylene by oxidation.

Thermal decomposition and isomerization of 1-Butyl and 1-Pentyl radical by flash pyrolysis vacuum ultraviolet photoionization time-of-flight mass spectrometry.

Thermal decomposition and isomerization of 1-butyl and 1-pentyl radical were studied in the temperature range of 500-1480 K on a short time scale of 20-100 µs using flash pyrolysis vacuum ultraviolet single-photon ionization time-of-flight mass spectrometry. 1-Bromobutane and 1-bromopentane were used as precursors for the 1-butyl and 1-pentyl radical, respectively. The reactive intermediates in the thermal dissociation reactions were directly observed. The 1-butyl radical decomposed to ethene and ethyl radical with ethyl radical rapidly losing an H atom to form a second ethene molecule. Loss of H atom from butyl radical was also a significant decomposition channel. Isomerization of 1-butyl via 1,3-H migration was observed as a minor channel at 1380 K and above with a branching ratio of less than 3% at 1430 K. The 1-pentyl radical was observed to decompose mainly by isomerization to 2-pentyl radical followed by β-scission to produce propene and ethyl radicals at temperatures approximately 900 K and below. Above 900 K, β-scission of 1-pentyl to produce ethene and 1-propyl radical became increasingly important. Isomerization to 3-pentyl was verified to be a minor channel.

On non‐hydrogen‐atom products of thermal decomposition of benzyl radical: A theoretical investigation by the transition state theory/multi‐well master equation approach

AbstractBenzyl radical (C7H7), one of the resonantly stabilized hydrocarbon radicals, is one of the significant precursors of polycyclic aromatic hydrocarbons in interstellar media and combustion engines. The unimolecular decomposition of benzyl radical is still incompletely understood despite of its importance and relatively small molecular size. The decomposition reactions of benzyl radical were investigated in the present study by using the ab initio transition state theory (TST) and the multi‐well master equation theory. Specifically, all reaction pathways on the potential energy surface of C7H7 was calculated at the level of QCISD(T)/CBS. For the reactions with multireference characters, the CASPT2(9e,7o)/aug‐cc‐pVTZ method was used to calculate the vibrational frequencies and energies of structures along the one‐dimensional reaction coordinate of the breaking bond. The high‐pressure limits of rate constants for all the reactions were obtained by using the TST except those for C7H6 + H and C6H4 + CH3 by the variational TST. The pressure‐dependent rate constants were obtained by using the multi‐well master equation simulations. The calculated rate constants agree well with available experimental and theoretical data in the literature. Moreover, the present results identify the composition of the non‐hydrogen‐atom production observed in previous experiments, which provide new insights into the reactions of aromatic compounds.

Experimental and reactive molecular dynamics simulation of municipal sludge extract pyrolysis

The sludge extract obtained from degradation solvent extraction exhibits high carbon content, low oxygen content, and ash-free characteristics, making it an ideal fuel due to its excellent performance. In this study, the pyrolysis process of the extract was systematically studied by combining GC-MS experiment with ReaxFF molecular dynamics simulation. The comparison between GC-MS experimental results and ReaxFF-MD simulation shows a high degree of similarity, thus confirming the accuracy of the simulation. This study identified 2000 K as the turning temperature between initial pyrolysis and secondary pyrolysis. In the temperature range of 1200–2000 K, the extract mainly undergoes primary pyrolysis, while in the temperature range of 2000–3000 K, the secondary reaction is remarkable, which is characterized by the further decomposition of tar free radicals and the condensation reaction involving tar free radicals or char. The analysis of typical gas content shows that H2, CO, NH3 and HCN are by-products of the secondary reaction of tar, and there are a lot of reducing gases at high temperature, such as H2, CO and CH4. Finally, the migration patterns of carbon, hydrogen, oxygen and nitrogen are discussed. It is worth noting that hydrogen and nitrogen mainly migrate to the pyrolysis gas phase. This not only laid a foundation for the separation of nitrogen and hydrogen in the future, but also triggered thinking about the potential of “low-carbon emission resource” in future research work. When compared to raw municipal sludge, the initial pyrolysis temperature of municipal sludge extract is much lower, and its pyrolysis process becomes faster. The advantages of reactive gas components indicate that it is more reactive. This variance results in a distinct product distribution and pyrolysis mechanism.

Emerging contaminants and pathogenic microorganisms elimination in secondary effluent by graphitic carbon nitride photocatalytic ozonation processes

The complexity of water contaminants, both chemical and biological requires an efficient and feasible treatment alternative. Herein, the photocatalytic ozonation treatment using graphitic carbon nitride catalysts was effectively applied for the elimination of a mixture of targeted chemical contaminants, and both Escherichia coli bacteria and Human polyomavirus JC (JC virus) in real secondary wastewater. The exfoliation treatment was compared in catalysts prepared using urea and melamine as precursors. The physical treatment provided no significant enhancement in the urea-based catalyst, while the improvement in the structure of the melamine-based (36MCN) material and formation of melem heterojunction increased its catalytic properties. In both sets of contaminants, the photocatalytic ozonation systems were superior to photolytic ozonation, especially regarding ozone consumption. The best catalyst, 36MCN, resulted in a decrease of 57.5%, 33.0% and 29.0% in the ozone dose required to eliminate chemical, bacteria and virus contaminants, respectively. The hydroxyl radicals were also shown as a key responsible for the pollutant’s elimination. The higher radical production and decomposition of ozone are possible indications of the better performance of graphitic carbon nitride photocatalytic ozonation, as an efficient tertiary wastewater alternative.

Interfacial polymerization mechanisms assisted flame retardancy process of low-flammable electrolytes on lithium anode

Thermal runaway is a hazardous risk, occurring more readily in high-energy–density lithium-ion batteries (LIBs), which leads to a rapid temperature rise and even combustion or explosion when using flammable electrolyte systems. Flame retardants (FRs), such as trimethyl phosphate (TMPa) and triethyl phosphate (TEP), are commonly utilized due to their effective flame suppression, low toxicity, and excellent thermal stability. However, the lack of in-depth understanding of the flame retardancy mechanism and solid electrolyte interphase (SEI) formation process has made the development of functional electrolytes difficult at present. In this study, we clarified the flame retardancy and interfacial reaction mechanisms of low-flammable TMPa localized high-concentration electrolytes (LHCE) using hybrid ab initio and reactive force field (HAIR) schemes. Long-term HAIR simulation reveals that phosphorous radicals produced by the decomposition of TMPa capture carbon radicals, encouraging their polymerization into low-flammable oligomers, while fluorine-containing solvents in the electrolyte capture hydrogen radicals and produce nonflammable hydrofluoric acid (HF). This synergistic flame retardancy mechanism provides essential atomic-level insights for the rational design of high-safety electrolytes in the future.

Theoretical study on low-temperature oxidation kinetics of methyl pentanoate

In order to develop reliable combustion models of biodiesel, the low-temperature oxidation kinetics of methyl pentanoate (MP), the smallest methyl ester with the negative temperature coefficient (NTC), is theoretically investigated. We use the DLPNO-CCSD(T)/CBS(T-Q)//M06-2X/cc-pVTZ and CASPT2/CBS(T-Q)//CASSCF(7e,5o)/cc-pVTZ methods to explore the potential energy surfaces (PESs) of the decomposition of different MP peroxy radicals, including dissociation, isomerization, and concerted HO2 elimination. Comparisons among the PESs of MP and other methyl esters reveal that the ester functional group inherently affects the low-temperature oxidation kinetics of methyl esters, and the energies of the species along the PESs are closely related to the active C site and the alkyl chain length. Based on the determined PESs, the pressure- and temperature-dependent rate constants for the low-temperature oxidation of MP are computed at 298−1200 K and 0.01−100 atm. The kinetic calculations suggest that the dissociation rate constants of different methyl ester peroxy radicals are similar at the same active C site, and the channels that lead to tri-molecular products are significant during the low-temperature oxidation of large methyl esters. The literature combustion model of MP is revised with our calculations. For the first time, the NTC behavior of MP is theoretically predicted by the revised model, and an excellent agreement between the predictions and the measurements reflects the reliability of the present low-temperature oxidation subset of MP.Novelty and Significance statementMethyl pentanoate (MP) is the smallest methyl ester with the negative temperature coefficient (NTC), but the low-temperature oxidation kinetics in the available combustion model of MP is still insufficient to interpret its NTC behavior. To develop a reliable combustion model for MP, the potential energy surfaces (PESs) of the decompositions of different MP peroxy radicals are investigated. Results show that the ester functional group inherently affects the low-temperature oxidation kinetics of methyl esters, and the energies of the species along the PESs are closely related to the active C site and the alkyl chain length. With our calculated rate constants, the literature combustion model is revised. For the first time, the NTC behavior of MP is theoretically predicted by the revised model, and an excellent agreement between the predictions and the measurements reflects the reliability of the present low-temperature oxidation subset of MP.

Theoretical study on iso‐pentanol oxidation chemistry: Fuel radical isomerization and decomposition kinetics and mechanism development

AbstractThis study undertakes a detailed theoretical investigation into the iso‐pentanol radical isomerization and decomposition kinetics and the mechanism development of the iso‐pentanol oxidation. The CCSD(T)/CBS//M08‐HX/6‐311+G(2df,2p) method was adopted to calculate the reaction potential energy surface. The reaction rate coefficients were calculated by variational transition state theory (VTST) with multistructural torsional (MS‐T) partition function and small curvature tunneling (SCT) correction. Moreover, the pressure‐dependent rate coefficients were determined using the system‐specific quantum Rice‐Ramsperger‐Kassel theory (SS‐QRRK). The variational and tunneling effects were discussed, and the dominant reaction channels were identified. It reveals that the isomerization reactions play a significant role at low temperatures, while the decomposition reactions dominate the high‐temperature regime. Notably, the quantitative rate expressions for iso‐pentanol radical decomposition reactions were also obtained. Furthermore, a new kinetic model incorporating the calculated rate coefficients was constructed, exhibiting satisfactory prediction performance on ignition delay times and improved predictive accuracy of species mole fractions. This work provides accurate rate data of isomerization and decomposition kinetics and contributes to a more comprehensive understanding of the iso‐pentanol oxidation mechanism.

Low-temperature ignition and oxidation mechanisms of tetrahydropyran

Cyclic ethers are relevant as next-generation biofuels and are also combustion intermediates that follow directly from unimolecular decomposition of hydroperoxyalkyl radicals. Accordingly, cyclic ether reactions are crucial to understanding low-temperature oxidation for advanced compression-ignition applications in combustion where peroxy radials are central to degenerate chain-branching pathways. Reaction mechanisms relevant to low-temperature ignition of cyclic ethers contain intrinsic complexities due to competing reactions of carbon-centered radicals formed in the initiation step undergoing either ring-opening or reactions with O2. To gain insight into mechanisms describing tetrahydropyran combustion, ignition delay time and speciation measurements were conducted. The present work integrates measurements below 1000 K of ignition delay times and species profiles in rapid compression machine experiments from 5 – 20 bar, spanning several equivalence ratios, with jet-stirred reactor experiments at 1 bar and stoichiometric conditions. The experiments are complemented with the development of the first chemical kinetics mechanism for tetrahydropyran that includes peroxy radical reactions, including O2-addition to tetrahydropyranyl (Ṙ), HOȮ-elimination from tetrahydropyranylperoxy (ROȮ) and hydroperoxytetrahydropyranyl (Q˙OOH), bi-cyclic ether formation, β-scission of Q˙OOH, and ketohydroperoxide formation.Negative-temperature coefficient (NTC) behavior is exhibited in the experiments and is reflected in the model predictions, which were within experimental uncertainty for several conditions. Disparities between the model predictions and experiments were analyzed via sensitivity analysis to identify contributing factors from elementary reactions. The analyses examine the role of ring-opening products of tetrahydropyranyl and hydroperoxytetrahydropyranyl isomers to identify reaction mechanisms that may contribute to model uncertainties. The detection of 66 species in the JSR experiments indicates that tetrahydropyran undergoes complex reaction networks, which includes interconnected reactions of aldehyde radicals and alkyl radicals. Primary radicals pentanal-5-yl and butanal-4-yl are derived from ring-opening reactions of tetrahydropyran-1-yl and undergo subsequent decarbonylation to form alkyl radicals (1-butyl and 1-propyl) that undergo reaction with O2 and may contribute to chain-branching, in addition to pathways involving tetrahydropyran-derived ketohydroperoxides.

Evaluation of the photosensitizer activity of hydrophobic phosphorus(V)porphyrins using the absorption spectral change of 1-benzyl-1,4-dihydronicotinamide

Under visible light irradiation, water-insoluble P(V)porphyrins oxidized 1-benzyl-1,4-dihydronicotinamide (BNADH), a model compound for nicotinamide adenine dinucleotide, and diminished the typical absorption of BNADH at around 340 nm. A singlet oxygen quencher, sodium azide, partially inhibited photosensitized BNADH oxidation. This BNADH oxidation photosensitized by P(V)porphyrins in the presence of sodium azide can be explained by electron transfer oxidation from BNADH to the photoexcited P(V)porphyrins. The quantum yields of BNADH oxidation via electron transfer by these P(V)porphyrins were larger than those of a singlet oxygen mechanism. Redox potential measurements supported the electron transfer mechanism from a thermodynamic point of view, and fluorescence lifetime measurement also suggests this mechanism. The process of this electron transfer oxidation involves the radical formation of BNADH and the further reaction of this radical to the oxidized form (cationic form of BNADH). Analysis of the quantum yields of BNADH photooxidation by P(V)porphyrins suggests that the photoinduced electron transfer from BNADH to photoexcited P(V)porphyrins triggers the radical chain reaction of BNADH oxidation. The electron transfer rate coefficient and this efficiency were increased with an increase in the Gibbs energy of electron transfer from tryptophan to photoexcited P(V)porphyrins (−ΔG). However, the BNADH oxidation quantum yield via electron transfer decreased with an increase in the -ΔG of electron transfer. These results suggest that reverse electron transfer inhibits the decomposition of BNAD radicals. This assay using BNADH can be used to evaluate the photosensitizer activity of water-insoluble compounds. These P(V)porphyrins may be used as photosensitizers for photodynamic therapy in a relatively hydrophobic environment in cancer tissues.

Reaction mechanism and kinetic modeling of gas-phase thermal decomposition of prototype nitramine compound HMX

The combustion, detonation, and explosion chemistry of energetic materials is regulated by the formation and decay of critical intermediates that are generated during the process. In this study, the pyrolysis mechanism of a commonly used cyclic nitramine explosive called octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine, also known as HMX or octogen, has been investigated by performing ab initio based RRKM/master equation analysis coupled with kinetic modeling simulations. The potential energy profiles of reaction network were constructed at the DLPNO-CCSD(T)/cc-pV[T,Q]Z level based on B3LYPD3/6-311+G(d,p) optimized geometries. The master equation calculations and kinetic modeling simulations indicated that the N-NO2 bond fission, leading to the formation of HMXR (the radical formed after NO2 loss) and nitro radicals, is the most important channel during the initial decomposition of HMX. The C-N and C-H β-scissions play an important role in the subsequent decomposition of the HMXR radical, with the C-H β-scission to form INT249 being the more favored consumption channel. Furthermore, this study also provided a preliminary exploration into the contribution of bimolecular reactions between HMX and H/OH/NO/NO2 radicals. The kinetic simulation results demonstrated that decomposition through these bimolecular reactions is of negligible importance under the investigated conditions.

Style-independent radical sequence learning for zero-shot recognition of Small Seal script

Small Seal script (Chinese called XiaoZhuan), as the earliest archaic form of standardized Chinese script, is the predecessor of modern Chinese characters. However, the Small Seal character recognition remains a challenging task, due to various un-/semi-structured pictographic glyphs and writing styles. This paper proposes a style-independent pictographic radical decomposition for the zero-shot recognition of Small Seal script, by taking advantage of the inherent consistency of pictographic representations between the Small Seal script and the Traditional Chinese script (Chinese called Fanti). Specifically, we design a feature-level collaboration framework of two tasks. One is the XiaoZhuan-to-Fanti translation task, which employs a generative adversarial network (GAN) based dual-learning mechanism to learn style-independent and consistent pictographic feature representations from different styles of Small Seal and their corresponding Traditional Chinese characters. The other is a transformer-based pictographic radical sequence learning from the pictographic feature representations. Experiments demonstrate that our model has satisfactory recognition ability to various styles of Small Seal scripts, especially for the zero-shot recognition of those with unknown glyphs and unseen styles. The code is available at https://github.com/windyz77/SmallSealRecon.

Interaction of acetylcholine with biodegradable biopolyesters and catalysis of the radical decomposition of hydroperoxides in solutions

Interaction of acetylcholine with biodegradable biopolyesters and catalysis of the radical decomposition of hydroperoxides in solutions