Chain Initiation Research Articles

Effect of CO2 on the explosion limit parameters and kinetic characteristics of ammonia-hydrogen-air mixtures

To explore the effect of CO2 on the explosion limit parameters and kinetic characteristics of the NH3-H2-air mixtures, the standard combustible gases explosion limits device was utilized to test and analyze the explosion limit, critical oxygen concentration, and explosion triangle. Based on the CHEMKIN software, the suppression mechanism of CO2 on NH3-H2-air mixtures explosion with 0.4 R (hydrogen ratio) and a near-inerting critical concentration was simulated and analyzed. The results indicated that increasing F (volume fraction of CO2) led to a decrease in the upper explosion limit (UEL) of NH3-H2-air mixtures and an increase in the lower explosion limit (LEL). When F increased to 36%, the explosion of the NH3-H2-air mixtures with 0.4 R was completely suppressed. As R increased, the UEL and LEL decreased and increased linearly, respectively, the critical explosion-suppression concentration of CO2 increased, the critical oxygen concentration decreased, and the explosive zone area also increased. In addition, based on the analysis of the changing characteristics of the UEL and LEL, prediction models for the UEL and LEL of NH3-H2-air mixtures with different hydrogen ratios under the effect of CO2 were provided. Reaction kinetics analysis found that less CO2 had a more pronounced impact on ·H and ·OH. However, when F increased to 20–30%, the maximum mole fraction of ·O decreased the most. At this point, the sensitivity of·NH2 towards decreasing oxygen concentrations became comparable to that of ·H and ·OH. When F increased to a near-critical explosion-suppression concentration of 30%, ·H, ·OH, ·O, and ·NH2 were in a critical state of disappearing, and the chain initiation of the explosion was destroyed. Sensitivity analysis indicated that ·H + O2(+M)<=>HO2(+M) and ·NH2+·NH=N2H3 performed a more significant inerting effect on ·H and ·NH2, which ultimately led to the termination of the explosive chain reactions.

Mechanism of methyl elaidate on the thermal oxidation behavior

The effects of cis–trans isomerization on the oxidation products of oleic acid (composites and structure characterization) were investigated. The reduction of thermal oxidation reaction of methyl elaidate (ME) was 6.72 % lower than that of methyl oleate (MO), and the oxidation products (core aldehydes) first increased and then decreased with the prolongation of thermal oxidation time. ME exhibited better oxidation stability than MO in free radicals, hydroperoxides, double bonds, aldehydes, and glycerides. The oxidation products were mainly 11-oxo-9-undecenoate (initial stage) and methyl 9-oxononanoate (later stage), following the free radical chain reaction mechanism. The H8 in double bond was more easily dehydrogenated in the chain initiation stage than H11, followed by the formation of core aldehyde through three intermediates and two transition states each pathway. ME required a higher energy barrier (1.3–13.6 kJ/mol) than MO reaction, making it more difficult for ME to undergo thermal oxidation reaction. The transition state 4 and 5 were rate determining steps of chain initiation reaction and proliferation reaction, respectively. This study was of great significance to further control the formation of these trans fats and their oxidation products.

Cooperative dynamics of PARP-1 zinc-finger domains in the detection of DNA single-strand breaks

The DNA single-strand break (SSB) repair pathway is initiated by the multifunctional enzyme PARP-1, which recognizes the broken DNA ends by its two zinc-finger domains, Zn1 and Zn2. Despite a number of experiments performed with different DNA configurations and reduced fragments of PARP-1, many details of this interaction that is crucial to the correct initiation of the repair chain are still unclear. We performed Molecular Dynamics (MD) computer simulations of the interaction between the Zn1/Zn2 domains of PARP-1 and a DNA hairpin including a missing nucleotide to simulate the presence of an SSB, a construct used in recent experiments. The role of Zn1 and Zn2 interacting with the SSB ends is studied in detail, both independently and cooperatively. We also explored, PARP-1 operating as a dimer, with the two Zn-fingers coming from two separate copies of the enzyme. By an extensive set of all-atom molecular simulations employing state-of-the art force fields, assisted by empirical docking and free-energy calculations, we conclude that the particular conformation of the DNA hairpin can indeed spontaneously open up by thermal fluctuations, up to extremely kinked deformations. However, such extreme localized deformations are rarely observed in free, long DNA fragments. Protein side-loops make contact with the DNA hairpin grooves, and help Zn2 to penetrate deep in the SSB gap. In this way, Zn2 can interact with the nucleotides opposite to the missing base. Overall, Zn1 plays a secondary role: the crucial factor for the interaction is rather the relative arrangement of the Zn1/Zn2 couple, and their mutual orientation with respect to the 3′\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$3'$$\\end{document} and 5′\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$5'$$\\end{document} SSB end terminals. This helps to obtain an early interacting configuration, which ultimately leads to molecular PARP-1-DNA structures similar to those observed experimentally. Such findings represent an important step toward defining the detailed function of PARP-1 in the early stages of SSB recognition.

Computational Study on the Inhibition Mechanisms of the Ziegler-Natta Catalyst in the Propylene Polymerization Process: Part 1 Effects of Acetylene and Methylacetylene

Acetylene and methylacetylene are impurities commonly found in the raw materials used for the production of polymers such as polypropylene and polyethylene. Experimental evidence indicates that both acetylene and methylacetylene can decrease the productivity of the Ziegler-Natta catalyst and alter the properties of the resulting polymer. However, there is still a lack of understanding regarding the mechanisms through which these substances affect this process. Therefore, elucidating these mechanisms is crucial to develop effective solutions to this problem. In this study, the inhibition mechanisms of the Ziegler-Natta catalyst by acetylene and methylacetylene are presented and compared with the incorporation of the first propylene monomer (chain initiation) to elucidate experimental effects. The Density Functional Theory (DFT) method was used, along with the B3LYP-D3 functional and the 6-311++G(d,p) basis set. The recorded adsorption energies were −11.10, −13.99, and −0.31 kcal mol−1, while the activation energies were 1.53, 2.83, and 28.36 kcal mol−1 for acetylene, methylacetylene, and propylene, respectively. The determined rate constants were 4.68 × 1011, 5.29 × 1011, and 2.3 × 10−8 M−1 s−1 for acetylene, methylacetylene, and propylene, respectively. Based on these values, it is concluded that inhibition reactions are more feasible than propylene insertion only if an ethylene molecule has not been previously adsorbed, as such an event reinforces propylene adsorption.

DFT Modeling of Coordination Polymerization of Polar Olefin Monomers by Molecular Metal Complexes

Introducing polar functional groups into polyolefin chains through polar olefin monomer coordination (co)polymerization can directly and significantly improve the surface properties of polymer materials and expand their application range. Therefore, the related research has always received considerable attention from both academia and industry. Many experimental studies have been reported in this field, and molecular metal complexes have shown high catalytic activity and selectivity in polar olefin monomer polymerizations. Although considerable DFT calculations have also been conducted for better understanding of the (co)polymerization performance, the factors governing the activity, selectivity, and molecular weight of resulting polymers are still ambiguous. This review mainly focuses on the DFT studies of polar olefin monomer coordination (co)polymerization catalyzed by molecular metal complexes in recent years, discussing the chain initiation and propagation, the origin of polymerization activity and selectivity, and the specific role of additives in the (co)polymerization reactions.

Mechanism and kinetics study of the chemically initiated oxidative polymerization of hexafluoropropylene

AbstractChemically initiated oxidative polymerization stands out as the most suitable method for the large‐scale and controllable synthesis of perfluoropolyether (PFPE). However, the mechanism and related reaction kinetics of this synthesis reaction remain elusive. In this study, PFPE was synthesized through the copolymerization of hexafluoropropylene and oxygen, initiated by fluorine. Subsequently, the synthesis mechanism of this chemically initiated oxidative polymerization was first explored using density functional theory. Simulation results yielded a comprehensive reaction network of the synthesis process, including chain initiation, propagation, decomposition, transfer, and termination. Meanwhile, a detailed kinetic model was constructed based on theoretical reaction rates of relevant elementary reactions. The effects of reaction operating conditions on the molecular weight of PFPE were experimentally investigated, with results in good agreement with the kinetic model. This work stablishes a solid foundation for optimizing and controlling the PFPE synthesis process.

Preparation of p-isopropylphenol polyoxyethylene ether and evaluation of its performance in concrete

P-isopropenylphenol polyoxylates (IPP-PE) were obtained by alkoxylation reaction using p-isopropylphenol phenol (IPP) and ethylene oxide (EO) as raw materials, and P-PCE polycarboxylic acid superplasticizer was obtained by free radical polymerization of ipp-PE and acrylic acid (AA) under the action of initiator and chain transfer agent. The effects of reaction temperature, acid-ether ratio, amount of chain transfer agent and initiator, and reaction time on the dispersion properties of superplasticizer were studied, and the molecular structure and microscopic morphology of the superplasticizer were characterized by FTIR,1HNMR, and SEM, and the influence of superplasticizer on concrete properties was evaluated by concrete performance tests. The test results determined that the optimal synthesis process of polycarboxylic acid superplasticizer was as follows: reaction temperature 40 °C, n(AA):n(IPP-PE)=6:1, chain transfer agent and initiator were 0.4% and 0.6% of the mass of large monomer, respectively, and the reaction time was 4.5h. The experimental results of the concrete performance test showed that the workability of concrete mixed with the self-made superplasticizer was excellent, and the initial and 1h longitudinal flowability of the superplasticizer reached 228 mm and 215 mm, respectively. The water reduction rate reached 36%, the 28d compressive strength reached 56.8 MPa, the initial slump reached 226 mm, and it had a certain retarding and air entrainment effect.

Study on the thermodynamic mechanism of external magnetic field on gas explosion characteristics

To investigate the thermodynamic mechanism of the magnetic field on the explosion characteristics of gases, experiments were carried out to study the influence of the applied magnetic field of 300 mT on the explosion characteristics of 5.7 % C2H6, 6.5 % C2H4 and 7.7 % C2H2 by volume. CHEMKIN-PRO software was used to simulate the three kinds of gas explosion chain reaction process. The chemical bond strength, stability and bond energy of the three gases were calculated and analyzed by Materials Studio software to derive the strength of chemical bond stability of the three gas molecules in the explosion process. The results show that the magnetic field weakened the breaking rate of CC, CC, and CC, the maximum explosion pressures of C2H6, C2H4, and C2H2 were reduced by 12.14 %, 16.47 %, and 18.71 %. The three gases carbon–carbon bond strength was weaker than the strength of the carbon-hydrogen bond, carbon-hydrogen bond was not easy to break, which in turn reduced the rate of generation of ·H in the chain initiation stage of the cleavage reaction, thus presenting a significant inhibitory effect of the magnetic field on C2H6, C2H4, and C2H2 explosions. The COOP of CC is 0.377 Ha, and the bond energy is 839 KJ/mol, which was greater than CC and CC, so the number of free radicals generated in the C2H2 cleavage reaction was lower, leading to a slower chain reaction rate which led to a stronger inhibitory effect of the magnetic field on C2H2 explosions than that on C2H6 and C2H4.

Theoretical Studies on the Insertion Reaction of Polar Olefinic Monomers Mediated by a Scandium Complex

This study aimed to investigate the insertion reaction of the polar monomers mediated by the cationic rare earth metal complex [(C5H5)Sc(NMe2CH2C6H4-o)]+ utilizing a combination of density functional theory (DFT) calculations and multivariate linear regression (MLR) methods. The chain initiation step of the insertion reaction could be described by the poisoning effect and the ease of monomer insertion, which could be represented via the DFT-calculated energy difference between σ- and π-coordination complexes (ΔΔE) and insertion energy barrier (ΔG≠), respectively. The results indicate that ΔΔE and ΔG≠ can be predicted by only several descriptors using multiple linear regression methods, with a root mean squared error (RMSE) of less than 2.5 kcal/mol. Furthermore, the qualitative analysis of the MLR models provided effective information on the key factors governing the insertion reaction chain initiation.

How to Improve the Curing Ability during the Vat Photopolymerization 3D Printing of Non-Oxide Ceramics: A Review.

Vat photopolymerization (VP), as an additive manufacturing process, has experienced significant growth due to its high manufacturing precision and excellent surface quality. This method enables the fabrication of intricate shapes and structures while mitigating the machining challenges associated with non-oxide ceramics, which are known for their high hardness and brittleness. Consequently, the VP process of non-oxide ceramics has emerged as a focal point in additive manufacturing research areas. However, the absorption, refraction, and reflection of ultraviolet light by non-oxide ceramic particles can impede light penetration, leading to reduced curing thickness and posing challenges to the VP process. To enhance the efficiency and success rate of this process, researchers have explored various aspects, including the parameters of VP equipment, the composition of non-oxide VP slurries, and the surface modification of non-oxide particles. Silicon carbide and silicon nitride are examples of non-oxide ceramic particles that have been successfully employed in VP process. Nonetheless, there remains a lack of systematic induction regarding the curing mechanisms and key influencing factors of the VP process in non-oxide ceramics. This review firstly describes the curing mechanism of the non-oxide ceramic VP process, which contains the chain initiation, chain polymerization, and chain termination processes of the photosensitive resin. After that, the impact of key factors on the curing process, such as the wavelength and power of incident light, particle size, volume fraction of ceramic particles, refractive indices of photosensitive resin and ceramic particles, incident light intensity, critical light intensity, and the reactivity of photosensitive resins, are systematically discussed. Finally, this review discusses future prospects and challenges in the non-oxide ceramic VP process. Its objective is to offer valuable insights and references for further research into non-oxide ceramic VP processes.

DECAF cross-device characterization of tokamak disruptions indicated by abnormalities in plasma vertical position and current

Abnormal (deviating from the target) variations in the plasma vertical position Z and current Ip (such as vertical displacements, transient Ip ‘spikes’ and quenches) constitute common elements of a disruption, a phenomenon that is to be mitigated, or ultimately avoided in future reactor-relevant tokamaks. While these abnormalities are generally recognized cross-shot and cross-device, details in terms of appearance (or not) and order of these abnormalities in disruption event chains (DEC) are bound to the plasma state at the time of the chain initiation. Detection of these abnormalities is thus indicative not only of the onset of the plasma collapse itself but also of the disruption driving cause that is promoted at a particular plasma state. Here, the occurrence of disruptions, explored via the detection of an Ip quench, and the analysis of DEC constituted by Ip and Z abnormalities is reported for in total seven full device-year pairs of operation of three machines (4, 2 and 1 years of KSTAR, MAST-U and NSTX-U operation, respectively) using the DECAF code expanded tools and capabilities. It is shown that the disruption occurrence depends not only on the details of the plasma state but also on (device-dependent) technical elements of the shot exit scenario. Year-to-year changes in the main disruption causes and a reduction in the disruptivity rate, bound by device and operation upgrades, are reported. Particular trigger instances of DEC (and the full chains when applicable) are shown to occupy different parts of the operation space diagrams, in accordance with prior expectations. Plasma elongation is identified as an important factor influencing details of the chains and its role will be further explored.

Nickel-Catalyzed Ethylene Copolymerization with Vinylalkoxysilanes: A Computational Study.

Since the discovery of α-diimine catalysts in 1995, an extensive series of Brookhart-type complexes have shown their excellence in catalyzing ethylene polymerizations with remarkable activity and a high molecular weight. However, although this class of palladium complexes has proven proficiency in catalyzing ethylene copolymerization with various polar monomers, the α-diimine nickel catalysts have generally exhibited a much worse performance in these copolymerizations compared to their palladium counterparts. Recently, Brookhart et al. reported a notable exception, demonstrating that α-diimine nickel catalysts could catalyze the ethylene copolymerization with some vinylalkoxysilanes effectively, producing functionalized polyethylene incorporating trialkoxysilane (-Si(OR)3) groups. This breakthrough is significant since Pd-catalyzed copolymerizations are commercially less usable due to the high cost of palladium. Thus, the utilization of Ni, given its abundance in raw materials and cost-effectiveness, is a landmark in ethylene/polar vinyl monomer copolymerization. Inspired by these findings, we used density functional theory (DFT) calculations to investigate the mechanistic study of ethylene copolymerization with vinyltrimethoxysilane (VTMoS) catalyzed by Brookhart-type nickel catalysts, aiming to elucidate the molecular-level understanding of this unique reaction. Initially, the nickel complexes and cationic active species were optimized through DFT calculations. Subsequently, we explored the mechanisms including the chain initiation, chain propagation, and chain termination of ethylene homopolymerization and copolymerization catalyzed by Brookhart-type complexes. Finally, we conducted an energetic analysis of both the in-chain and chain-end of silane enchainment. It was found that chain initiation is the dominant step in the ethylene homopolymerization catalyzed by the α-diimine Ni complex. The 1,2- and 2,1-insertion of vinylalkoxysilane exhibit similar barriers, explaining the fact that both five-membered and four-membered chelates were identified experimentally. After the VTMoS insertion, the barriers of ethylene reinsertion become higher, indicating that this step is the rate-determining step, which could be attributed to the steric hindrance between the incoming ethylene and the bulky silane substrate. We have also reported the energetic analysis of the distribution of polar substrates. The dominant pathway of chain-end -Si(OR)3 incorporation is suggested as chain-walking → ring-opening → ethylene insertion, and the preference of chain-end -Si(OR)3 incorporation is primarily attributed to the steric repulsion between the pre-inserted silane group and the incoming ethylene molecule, reducing the likelihood of in-chain incorporation.

The tandem catalysis of porous CoW composite oxide: Intensified allylic oxidation of cyclohexene to 2-cyclohexene-1-one

The controllable oxidation of the allylic CH bond has great academic and industrial value. Different Co/W ratios of CoW composite oxides were prepared using hydrothermal method and used in the allylic oxidation reaction of cyclohexene containing unstable allylic hydrogen atoms and carbon-carbon double bonds. The relationship between the structure of active sites and catalytic performance was revealed using characterization techniques such as XRD, N2 adsorption/desorption, SEM, TEM, FT-IR, UV–vis, and XPS. The results indicated that the Co(II)/Co(III) sites effectively mediate the first step of the entire oxidation reaction system, which generates hydroxyl radicals and peroxyl radicals through the activation of H2O2 to achieve chain initiation. Subsequently, the cyclohexene underwent a series of chain migration reactions under the action of hydroxyl radicals and peroxyl radicals, resulting in the formation of 2-cyclohexen-1-one and 2-cyclohexen-1-ol. Finally, 2-cyclohexen-1-ol interacted with W(VI) sites to form 2-cyclohexen-1-one via an alcohol-coordinated hydroxyl intermediate. The tandem oxidation reaction of cyclohexene allylic oxidation and 2-cyclohexen-1-ol dehydrogenation was realized by the CoW synergistic catalytic. The synergy between Co and W sites, composed of Co-O-W units on the surface of the CoW oxide with porous channel features, was elucidated. The experimental results showed that under the optimal conditions, using CoW composite oxide (Co/W = 1:1) as the catalyst, a 79.8% conversion rate of cyclohexene was achieved with 93.9% selectivity for the allylic products, among which the selectivity for 2-cyclohexen-1-one was 73.8%.

Unveiling the Detailed Mechanism and Origins of Chemo-, Regio-, and Stereoselectivity of Rare-Earth Catalyzed Alternating Copolymerization of Polar and Nonpolar Olefins.

The direct copolymerization of polar and nonpolar olefins is of great interest and significance, as it is the most atom-economical and straightforward strategy for the synthesis of functional polyolefin materials. Despite considerable efforts, the precise control of monomer-sequence and their regio- and stereochemistry is full of challenges, and the related mechanistic origins are still in their infancy to date. Herein, the mechanistic studies on the model reaction of Sc-catalyzed co-syndiospecific alternating copolymerization of anisylpropylene (AP) and styrene were performed by DFT calculations. The results suggest that the subtle balance between electronic and steric factors plays an important role during monomer insertions, and a new amino-dissociated mechanism was proposed for AP insertion at chain initiation. AP insertion follows the 2,1-si-insertion pattern, which is mainly controlled by steric factors caused by the restricted MeO···Sc interaction. As for styrene insertion, it prefers the 2,1-re-insertion manner and its regio- and stereoselectivities are influenced by steric repulsions between the inserting styrene and the polymer chain or the ligand. More interestingly, it is found that the alternating monomer-sequence is mainly determined by the "steric matching" principle, which is quantitatively expressed by the buried volume of the metal center of the preinserted species. The concept of steric pocket has been successfully applied to explain the different performances of several catalysts and other alternating copolymerization reactions. The insightful mechanistic findings and the quantitative steric pocket model present here are expected to promote rational design of new rare-earth catalysts for developing regio-, stereo-, and sequence-controlled copolymerization of specific polar and nonpolar olefins.

Novel kinetic modeling strategy for industrial-scale UNIPOL polypropylene with Ziegler-Natta catalyst

Polypropylene (PP) is a synthetic resin with exceptional physical and chemical properties, making it suitable for various household and industrial applications. However, as the demand for PP continues to rise, the polypropylene industry faces challenges in improving its quality and efficiency. Developing an accurate mathematical model that describes the continuous polymerization process is crucial for enhancing PP production, as it is useful for controlling product quality and improving production efficiency. While previous studies have focused on modeling propylene polymerization using laboratory-scale and pilot-scale reactors, these models do not effectively apply to industrial-scale processes due to the complexity of the industrial environment. Therefore, a novel kinetic modeling method combining the modeling of the kinetic mechanism of the polymerization reaction with an intelligent optimization algorithm for the industrial-scale continuous gas-phase fluidized bed propylene polymerization process is proposed. To establish the kinetic mechanism model, the improved moments (MOM) method is utilized to derive a set of mass balance equations that account for various fundamental processes such as catalyst activation, chain initiation, chain growth, chain transfer to hydrogen, chain transfer to monomers, chain transfer to co-catalysts, and spontaneous deactivation. However, kinetic parameters serve as the link between the theoretical model and the actual production process, so the kinetic parameters estimation problem need to be transformed into a multi-objective problem by minimizing the least squares difference between the measurement data of the actual industry process and the predicted result of the kinetic model. Therefore, an improved multi-objective mayfly algorithm (IMOMA) is introduced to estimate the polymerization kinetic parameters, which incorporates the simulated binary crossover (SBX) operator and the polynomial mutation (PM) operator into the basic multi-objective mayfly algorithm (MOMA). Finally, by fitting industrial measurement data of the melt index (MI) and the polymerization rate (PR) of an actual polypropylene industrial case study, the proposed algorithm accurately determines the polymerization kinetic parameters. The results demonstrate that the MOM-IMOMA modeling approach outperforms other methods and holds significant promise for industrial-scale polypropylene production.

Mechanism of cationic ring-opening polymerisation of ε-caprolactone using metallocene/borate catalytic systems: a DFT and NCI study on chain initiation, propagation and termination.

We present a comprehensive DFT investigation on the cationic ring-opening polymerisation (CROP) of ε-caprolactone (CL) using zirconocene/borate catalyst systems. All possible pathways of the interaction between cationic species [Cp2ZrMe+] and counteranions, [A-] = [MeB(C6F5)3]- and [B(C6F5)4]-, were examined during chain initiation, propagation, and termination steps. The calculations reveal an active chain-end mechanism with O-alkyl bond cleavage of the polymerisation. The catalytic performance of the two counteranions is found to be identical, and they influence the initial process through stabilisation of the cationic species via non-covalent interactions (NCI), with the [MeB(C6F5)3]- anion stabilising the catalyst-monomer complex more effectively than the [B(C6F5)4]- anion by 24.3 kJ mol-1. The first two propagations are likely the rate-determining step, with calculated free-energy barriers of 61.4-71.2 and 73.9-80.6 kJ mol-1 with and without the anions (A-), respectively. The presence of the counteranion significantly affects the third propagation rate, lowering the barriers up to 20 kJ mol-1. Comparison of the first termination and the third propagation shows that they are not competitive, with the termination being less facile. We also studied the initiation and propagation steps for the hafnocene catalyst and found that the Hf catalyst slightly favours the CL CROP in comparison to the Zr catalyst. Analysis of solvent and dispersion interaction demonstrates that both factors play an important role in the process. NCI analysis reveals weak (van der Waals) interactions at the contacts between the cationic species and the counteranions during the reaction course. Overall, our results offer insights into the structures and interactions involved in the polymerisation.

Revealing the low to moderate temperature oxidation kinetics of 1,2,4-trimethylbenzene sensitized by dimethyl ether

Low to moderate temperature oxidation has been a vital topic in the combustion chemistry due to its critical role in controlling the combustion characteristics such as autoignition and pollutant emissions. Low temperature oxidation kinetics of alkanes and oxygenated biofuels have been widely explored, while that of branched aromatics is poorly understood. This work aims to investigate the low to moderate temperature oxidation kinetics of 1,2,4-trimethylbenzene (TMB, C9H12), which is a multi-branched alkylbenzene with weak low temperature oxidation reactivity. To enhance the low temperature oxidation reactivity of TMB, dimethyl ether (DME) was added to efficiently provide chain initiators. The oxidation experiment of TMB/DME mixture was performed with an atmospheric jet stirred reactor coupled with synchrotron vacuum ultraviolet radiation photoionization mass spectrometry. The negative temperature coefficient (NTC) behavior, as well as featured aromatic intermediates, especially phenyl hydroperoxides and unexpected highly oxygenated molecules (HOMs), were observed in the experiment. The detection of these fingerprint aromatic intermediates provide crucial evidence for revealing the low to moderate oxidation kinetics of TMB. In addition, a kinetic model was developed to provide in-depth kinetic analysis. The results demonstrate that the active chain initiators produced from DME oxidation trigger the low temperature chain-branching reactions of TMB. The chain recycling process is further sustained due to the regeneration of active intermediates such as phenyl hydroperoxides and •OH radicals. Aromatic intermediates with chemical compositions of C9H12Ox and C9H10Ox were measured and identified to be key indicators for the low temperature chemistry of TMB. In particular, the aromatic HOMs (C9H12O6 and C9H10O5) are fingerprint intermediates produced from the third O2 addition and subsequent reactions of TMB. Besides, the sensitivity analysis indicates that the interaction kinetics between TMB and DME by sharing the highly sensitive reactions of hydroperoxides and •OH radicals. The present work extends the conceptual reaction schemes proposed in alkanes towards branched aromatics, especially sequential O2 addition reactions that contributing to the formation of phenyl hydroperoxides and HOMs.

Using Mechanochemistry to Activate Commodity Plastics as Initiators for Radical Chain Reactions of Small Organic Molecules.

Radical initiators such as azo compounds and organic peroxides have been widely used to facilitate numerous transformations of free radicals, which enable the efficient synthesis of structurally complex molecules, natural products, polymers, and functional materials. However, these high-energy reagents are potentially explosive and thus often require special precautions or delicate operating conditions. We postulated that a more convenient and safer alternative for radical chain initiation could be developed by mechanical activation of thermodynamically stable covalent bonds. Here, we show that commodity plastics such as polyethylene and poly(vinyl acetate) are capable of acting as efficient initiators for radical chain reactions under solvent-free mechanochemical conditions. In this approach, polymeric mechanoradicals, which are generated by homolytic cleavage of the polymer chains in response to the applied mechanical energy provided by ball milling, react with tris(trimethylsilyl)silane to initiate radical chain dehalogenation of organic halides. Preliminary calculations support our proposed force-induced radical chain mechanism.

A unique dual acyltransferase system shared in the polyketide chain initiation of kidamycinone and rubiflavinone biosynthesis.

The pluramycin family of natural products has diverse substituents at the C2 position, which are closely related to their biological activity. Therefore, it is important to understand the biosynthesis of C2 substituents. In this study, we describe the biosynthesis of C2 moieties in Streptomyces sp. W2061, which produces kidamycin and rubiflavinone C-1, containing anthrapyran aglycones. Sequence analysis of the loading module (Kid13) of the PKS responsible for the synthesis of these anthrapyran aglycones is useful for confirming the incorporation of atypical primer units into the corresponding products. Kid13 is a ketosynthase-like decarboxylase (KSQ)-type loading module with unusual dual acyltransferase (AT) domains (AT1-1 and AT1-2). The AT1-2 domain primarily loads ethylmalonyl-CoA and malonyl-CoA for rubiflavinone and kidamycinone and rubiflavinone, respectively; however, the AT1-1 domain contributed to the functioning of the AT1-2 domain to efficiently load ethylmalonyl-CoA for rubiflavinone. We found that the dual AT system was involved in the production of kidamycinone, an aglycone of kidamycin, and rubiflavinone C-1 by other shared biosynthetic genes in Streptomyces sp. W2061. This study broadens our understanding of the incorporation of atypical primer units into polyketide products.

Mechanistic Studies on Aluminum-Catalyzed Ring-Opening Alternating Copolymerization of Maleic Anhydride with Epoxides: Ligand Effects and Quantitative Structure-Activity Relationship Model.

Previous work has indicated that aluminum (Al) complexes supported by a bipyridine bisphenolate (BpyBph) ligand exhibit higher activity in the ring-opening copolymerization (ROCOP) of maleic anhydride (MAH) and propylene oxide (PO) than their salen counterparts. Such a ligand effect in Al-catalyzed MAH-PO copolymerization reactions has yet to be clarified. Herein, the origin and applicability of the ligand effect have been explored by density functional theory, based on the mechanistic analysis for chain initiation and propagation. We found that the lower LUMO energy of the (BpyBph)AlCl complex accounts for its higher activity than the (salen)AlCl counterpart in MAH/epoxide copolymerizations. Inspired by the ligand effect, a structure-energy model was further established for catalytic activity (TOF value) predictions. It is found that the LUMO energies of aluminum chloride complexes and their average NBO charges of coordinating oxygen atoms correlate with the catalytic activity (TOF value) of Al complexes (R2 value of 0.98 and '3-fold' cross-validation Q2 value of 0.88). This verified that such a ligand effect is generally applicable in anhydride/epoxide ROCOP catalyzed by aluminum complex and provides hints for future catalyst design.