Search Results (20)

The steady smoldering of rod-shaped fuels, a traditional Chinese disinfection and pest control technique, presents unique challenges in theoretical modeling. Conventional analytical approaches based on energy and mass conservation equations form an underdetermined system, failing to uniquely resolve three critical parameters: temperature field, char morphology, and propagation velocity. This study establishes a quantitative relationship between smoldering propagation velocity and smoke schlieren thickness through integrated experimental and theoretical methodologies. Systematic experiments were conducted on vertically oriented fuel rods (upward and downward configurations), measuring propagation velocity, char cone geometries, and schlieren photographs. By incorporating surface oxidation kinetics and oxygen transport mechanisms into a theoretical model, we revealed an inverse proportionality between propagation velocity and schlieren thickness, thereby introducing a third constraint to resolve the system. Comparative analysis demonstrated excellent agreement between calculated and measured velocities for downward smoldering, with deviations below 20% for biomass rods and 60% for commercial incense rods. Significant discrepancies in upward smoldering were attributed to smoke plume entrainment effects. This work enhances the mechanistic understanding of smoldering propagation dynamics in anisotropic fuel systems. Full article

The polymerization mechanism of para-methoxystyrene catalyzed by cationic α-diimine palladium complexes with various ancillary ligands was rigorously examined using density functional theory. In the classical methyl-based α-diimine palladium complex [{(2,6-ⁱPr₂C₆H₃)-N=C(Me)-C(Me)=N-2,6-ⁱPr₂C₆H₃)}PdMe]⁺ (A⁺), the 2,1-insertion of para-methoxystyrene is favored over the 1,2-insertion, both thermodynamically and kinetically, during the chain initiation step. The resulting thermodynamically favored η³-π-benzyl intermediates face a substantial energy barrier, yielding only trace amounts of polymer, as experimentally verified. In contrast, the dibenzobarrelene-based α-diimine palladium complex [{(2,6-ⁱPr₂C₆H₃)-N=C(R)-C(R)=N-2,6-ⁱPr₂C₆H₃)}PdMe]⁺ (R = dibenzobarrelene, B⁺) shows similar energy barriers for both 2,1- and 1,2-insertions. Continuous 2,1/2,1 or 2,1/1,2 insertions are impeded by excessive energy barriers. However, theoretical calculations reveal that the 1,2-insertion product can seamlessly transition into the chain propagation stage, producing a polymer with high 1,2-regioselectivity. The observed activity of complexes A⁺ or B⁺ towards para-methoxystyrene polymerization stems from the energy barrier differences between the 1,2- and 2,1-insertions, influenced by the steric hindrance from the ancillary ligands. Further investigation into the effects of steric hindrance on the chain initiation stage involved computational modeling of analogous complexes with increased steric bulk. These studies established a direct correlation between the energy barrier difference ∆∆G (1,2–2,1) and the van der Waals volume of the ancillary ligand. Larger van der Waals volumes correspond to reduced energy barrier differences, thus enhancing the regioselectivity for para-methoxystyrene polymerization. Moreover, the experimental inertness of complex B⁺ towards styrene polymerization is attributed to the formation of stable kinetic and thermodynamic 2,1-insertion intermediates, which obstruct further styrene monomer insertion due to an extremely high reactive energy barrier. These findings contribute to a deeper understanding of the mechanistic aspects and offer insights for designing new transition metal catalysts for the polymerization of para-alkoxystyrenes. Full article

Aminoacetaldehyde (glycinal, NH₂CH₂CHO) is a first-generation oxidation product of monoethanolamine (MEA, NH₂CH₂CH₂OH), a solvent widely used for CO₂ gas separation, which is proposed as the basis for a range of carbon capture technologies. A complete oxidation mechanism for MEA is required to understand the atmospheric transformation of carbon capture plant emissions, as well as the degradation of this solvent during its use and the oxidative destruction of waste solvent. In this study, we have investigated the ^•OH radical-initiated oxidation chemistry of aminoacetaldehyde using quantum chemical calculations and RRKM theory/master equation kinetic modeling. This work predicts that aminoacetaldehyde has a tropospheric lifetime of around 6 h and that the reaction predominantly produces the NH₂CH₂C^•O radical intermediate at room temperature, along with minor contributions from NH₂^•CHCHO and ^•NHCH₂CHO. The dominant radical intermediate NH₂CH₂C^•O is predicted to promptly dissociate to NH₂^•CH₂ and CO, where NH₂^•CH₂ is known to react with O₂ under tropospheric conditions to form the imine NH = CH₂ + HO₂. The NH₂^•CHCHO radical experiences captodative stabilization and is found to form a weakly bound peroxyl radical upon reaction with O₂. Instead, the major oxidation product of NH₂^•CHCHO and the aminyl radical ^•NHCH₂CHO is the imine NH = CHCHO (+HO₂). In the atmosphere, the dominant fate of imine compounds is thought to be hydrolysis, where NH = CH₂ will form ammonia and formaldehyde, and NH = CHCHO will produce ammonia and glyoxal. Efficient conversion of the dominant first-generation oxidation products of MEA to ammonia is consistent with field observations and supports the important role of imine intermediates in MEA oxidation. Full article

Reaction OH + OCS → products (1) has been studied in a discharge–flow reactor combined with modulated molecular beam mass spectrometry. The reaction rate constant has been determined under pseudo-first-order conditions through monitoring OH decays in a high excess of OCS: k₁ = (2.35 ± 0.25) × 10⁻¹² exp(−(2144 ± 56)/T) cm³ molecule⁻¹ s⁻¹ at T = 365–960 K (the uncertainties represent precision at the 2σ level, the total 2σ relative uncertainty including statistical and systematic errors on the rate constant being 20% at all temperatures). The rate constant of reaction (1) was found to be similar at a total helium pressure of 1, 2, and 8 torr at around 500 K. The SH radical was identified as the primary product of the reaction, and its yield was determined to be about 100% at T = 500 and 750 K. The kinetic and mechanistic data from the present study are compared to previous experimental and theoretical work. Full article

The aim of this work is to synthesize and characterize alginate–Moroccan clay bio-composite in order to improve our understanding of the adsorption of inorganic pollutants found in textile effluents. Characterization of the bio-composite used was carried out using a variety of techniques (IR-TF, SEM, DRX, and pH_ZPC). The influence of the medium’s physico-chemical parameters (temperature, pH, initial concentration, etc.) on the retention of inorganic pollutants was also studied. Studies of adsorption and inorganic pollutants such as orthophosphate (H₂PO₄⁻ and HPO₄²⁻) and nitrate (NO₃⁻) ions were carried out, using simple solutions from the laboratory, in a batch system. This study explored the impact of adsorbent dose, contact time, solution pH, and temperature on the adsorption process. Various kinetic models, including pseudo-first-order, pseudo-second-order, intra-particle diffusion, and Elovich models, were tested and evaluated, to illustrate the adsorption kinetics. This study’s findings demonstrated that the adsorption process follows second-order kinetics, with associated rate constants successfully determined. The correlation coefficient for the pseudo-second-order kinetic model is nearly equal to 1 (>0.98), and the value of theoretical adsorption capacity (q_e,the) is comparable to the experimental one (q_e,the = 58.14 mg/g for H₂PO₄⁻, q_e,the = 54.64 mg/g for HPO₄²⁻, and q_e,the = 52.63 mg/g for NO₃⁻). Additionally, the adsorption equilibrium was investigated through the application of various mathematical models, including the Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich isotherm models, to assess the mechanistic parameters associated with the adsorption process. Among these models, the Langmuir isotherm emerged as the most suitable one for characterizing the adsorption of H₂PO₄⁻, HPO₄²⁻, and NO₃⁻ ions using bio-nanocomposite beads. The maximum adsorbed amounts of metal ions by the bio-nanocomposite used were 625 mg/g for H₂PO₄⁻, 909.09 mg/g for HPO₄²⁻, and 588.23 mg/g for NO₃⁻ from the batch system. The endothermic and physical nature of the adsorption is suggested by the positive values of ΔH°, which is consistent with experimental findings. The adsorption process is spontaneous, as evidenced by the negative ΔG° values. Positive ΔS° values indicate increased randomness at the solid/liquid interface during adsorption of ion-organic ions onto the engineered bio-nanocomposite. The obtained results demonstrated that, from a scientific perspective, alginate–Moroccan clay bio-nanocomposites exhibit a highly significant adsorption capability for the removal of oxyanions in aqueous environments. Full article

As an important cancer therapeutic target, extracellular signal-regulated kinases (ERK) are involved in triggering various cellular responses in tumors. Regulation of the ERK signaling pathway by the small molecular inhibitors is highly desired for the sake of cancer therapy. In contrast to the routine inhibitors targeting ERKs through long-range non-bonding interactions, Ponatinib, a covalent inhibitor to ERK2 with a macrocyclic structure characterized by the α,β-C=C unsaturated ketone, can form the stable -C(S)-C(H)-type complex via the four-center barrier due to the nucleophilic addition reaction of the thiol group of the Cys166 residue of ERK2 with the C=C double bond of Ponatinib with reaction free-energy barrier of 47.2 kcal/mol. Reaction mechanisms for the covalent binding were calculated using QM/MM methods and molecular dynamics simulations. The interaction modes and the corresponding binding free energies were obtained for the non-covalent and covalent complexation. The binding free energies of the non-covalent and covalent inhibitions are 14.8 kcal/mol and 33.4 kcal/mol, respectively. The mechanistic study stimulated a rational design on the modified Ponatinib structure by substituting the C=C bond with the C=N bond. It was demonstrated that the new compound exhibits better inhibition activity toward ERK2 in term of both thermodynamic and kinetic aspects through the covalent binding with a lower reaction free-energy barrier of 23.1 kcal/mol. The present theoretical work sheds new light on the development of the covalent inhibitors for the regulation of ERKs. Full article

(1) Background: the theoretical modelling of reactions occurring in liquid phase is a research line of primary importance both in theoretical–computational chemistry and in the context of organic and biological chemistry. Here we present the modelling of the kinetics of the hydroxide-promoted hydrolysis of phosphoric diesters. (2) Method: the theoretical–computational procedure involves a hybrid quantum/classical approach based on the perturbed matrix method (PMM) in conjunction with molecular mechanics. (3) Results: the presented study reproduces the experimental data both in the rate constants and in the mechanistic aspects (C–O bond vs. O–P bond reactivity). The study suggests that the basic hydrolysis of phosphodiesters occurs through a concerted $A_N{D}_N$ mechanism, with no formation of penta-coordinated species as reaction intermediates. (4) Conclusions: the presented approach, despite the approximations, is potentially applicable to a large number of bimolecular transformations in solution and therefore leads the way to a fast and general method to predict the rate constants and reactivities/selectivities in complex environments. Full article

Chlorophenols (CPs) and phenol are abundant in thermal and combustion procedures, such as stack gas production, industrial incinerators, metal reclamation, etc., which are key precursors for the formation of polychlorinated naphthalenes (PCNs). CPs and phenol can react with H or OH radicals to form chlorophenoxy radicals (CPRs) and phenoxy radical (PhR). The self-condensation of CPRs or cross-condensation of PhR with CPRs is the initial and most important step for PCN formation. In this work, detailed thermodynamic and kinetic calculations were carried out to investigate the PCN formation mechanisms from PhR with 2-CPR/3-CPR. Several energetically advantageous formation pathways were obtained. The rate constants of key elementary steps were calculated over 600~1200 K using the canonical variational transition-state theory (CVT) with the small curvature tunneling (SCT) contribution method. The mechanisms were compared with the experimental observations and our previous works on the PCN formation from the self-condensation of 2-CPRs/3-CPRs. This study shows that naphthalene and 1-monochlorinated naphthalene (1-MCN) are the main PCN products from the cross-condensation of PhR with 2-CPR, and naphthalene and 2-monochlorinated naphthalene (2-MCN) are the main PCN products from the cross-condensation of PhR with 3-CPR. Pathways terminated with Cl elimination are preferred over those terminated with H elimination. PCN formation from the cross-condensation of PhR with 3-CPR can occur much easier than that from the cross-condensation of PhR with 2-CPR. This study, along with the study of PCN formation from the self-condensation 2-CPRs/3-CPRs, can provide reasonable explanations for the experimental observations that the formation potential of naphthalene is larger than that of 1-MCN using 2-CP as a precursor, and an almost equal yield of 1-MCN and 2-MCN can be produced with 3-CP as a precursor. Full article

The regioselective zw-type [3 + 2] cycloaddition (32CA) reactions of a series of aryl-substituted nitrile N-oxides (NOs) with trichloronitropropene (TNP) have been both experimentally and theoretically studied within the Molecular Electron Density Theory (MEDT). Zwitterionic NOs behave as moderate nucleophiles while TNP acts as a very strong electrophile in these polar 32CA reactions of forward electron density flux, which present moderate activation Gibbs free energies of 22.8–25.6 kcal·mol⁻¹ and an exergonic character of 28.4 kcal·mol⁻¹ that makes them irreversible and kinetically controlled. The most favorable reaction is that involving the most nucleophilic MeO-substituted NO. Despite Parr functions correctly predicting the experimental regioselectivity with the most favorable O-CCCl₃ interaction, these reactions follow a two-stage one-step mechanism in which formation of the O-C(CCl₃) bond takes place once the C-C(NO₂) bond is already formed. The present MEDT concludes that the reactivity differences in the series of NOs come from their different nucleophilic activation and polar character of the reactions, rather than any mechanistic feature. Full article

A challenge in the field of polymer network synthesis by a step-growth mechanism is the quantification of the relative importance of inter- vs. intramolecular reactions. Here we use a matrix-based kinetic Monte Carlo (kMC) framework to demonstrate that the variation of the chain length distribution and its averages (e.g., number average chain length x_n), are largely affected by intramolecular reactions, as mostly ignored in theoretical studies. We showcase that a conventional approach based on equations derived by Carothers, Flory and Stockmayer, assuming constant reactivities and ignoring intramolecular reactions, is very approximate, and the use of asymptotic limits is biased. Intramolecular reactions stretch the functional group (FG) conversion range and reduce the average chain lengths. In the likely case of restricted mobilities due to diffusional limitations because of a viscosity increase during polymerization, a complex x_n profile with possible plateau formation may arise. The joint consideration of stoichiometric and non-stoichiometric conditions allows the validation of hypotheses for both the intrinsic and apparent reactivities of inter- and intramolecular reactions. The kMC framework is also utilized for reverse engineering purposes, aiming at the identification of advanced (pseudo-)analytical equations, dimensionless numbers and mechanistic insights. We highlight that assuming average molecules by equally distributing A and B FGs is unsuited, and the number of AB intramolecular combinations is affected by the number of monomer units in the molecules, specifically at high FG conversions. In the absence of mobility constraints, dimensionless numbers can be considered to map the time variation of the fraction of intramolecular reactions, but still, a complex solution results, making a kMC approach overall most elegant. Full article

Olefins are among the most important structural building blocks for a plethora of chemical reaction products, including petrochemicals, biomaterials and pharmaceuticals. An ever-increasing economic demand has urged scientists, engineers and industry to develop novel technical methods for the dehydrogenation of parent alkane molecules. In particular, the catalysis over precious metal or metal oxide catalysts has been put forward as an alternative way route to thermal-, steam- and fluid catalytic cracking (FCC). Multiscale system modeling as a tool to theoretically understand processes has in the past decade period evolved from a rudimentary measurement-complementing approach to a useful engineering environment. Not only can it predict various experimentally obtained parameters, such as conversion, activity, and selectivity, but it can help us to simulate trends, when changing applicative operating conditions, such as surface gas temperature or pressure, or even support us in the search for the type of materials, their geometrical properties and phases for a better functional performance. An overview of the current set state of the art for saturated organic short chain hydrocarbons (ethane, propane and butane) is presented. Studies that combine at least two different dimensional scales, ranging from atomistic-, bridging across mechanistic mesoscale kinetics, towards reactor- or macroscale, are focused on. Insights considering reactivity are compared. Full article

Soybean peroxidase is an enzyme extracted from soybean seed hulls. In the presence of hydrogen peroxide, the enzyme has the potential to catalyze the biodegradation of toxic substances like chlorophenols. For this reason, its use in wastewater treatment processes is environmentally friendly since the enzyme can be obtained from a renewable and abundant raw material. In this work, enzymatic biodegradation of 2,4,6-trichlorophenol performed by soybean peroxidase in a microreactor was studied experimentally and theoretically. The experimental data set was obtained with a volume of 250 μL by using different soybean peroxidase concentrations and different reaction times. The fluid dynamics of the microreactor was modeled as well, using ANSYS CFX. The simulations exhibited secondary flows, which enhanced mixing. Although the laminar flow was developed, it can be assumed to be a well-mixed medium. The kinetic data were evaluated through a mechanistic model, the modified bi-bi ping-pong model, which is adequate to represent the enzymatic degradation using peroxidases. The model was composed of an initial value problem for ordinary differential equations that were solved using MATLAB. Some kinetic constants were estimated using the least square function. The results of the model fit well the experimental data. Full article

Direct propylene epoxidation using Au-based catalysts is an important gas-phase reaction and is clearly a promising route for the future industrial production of propylene oxide (PO). For instance, gold nanoparticles or clusters that consist of a small number of atoms demonstrate unique and even unexpected properties, since the high ratio of surface to bulk atoms can provide new reaction pathways with lower activation barriers. Support materials can have a remarkable effect on Au nanoparticles or clusters due to charge transfer. Moreover, Au (or Au-based alloy, such as Au–Pd) can be loaded on supports to form active interfacial sites (or multiple interfaces). Model studies are needed to help probe the underlying mechanistic aspects and identify key factors controlling the activity and selectivity. The current theoretical/computational progress on this system is reviewed with respect to the molecular- and catalyst-level aspects (e.g., first-principles calculations and kinetic modeling) of propylene epoxidation over Au-based catalysts. This includes an analysis of H₂ and O₂ adsorption, H₂O₂ (OOH) species formation, epoxidation of propylene into PO, as well as possible byproduct formation. These studies have provided a better understanding of the nature of the active centers and the dominant reaction mechanisms, and thus, could potentially be used to design novel catalysts with improved efficiency. Full article

A detailed mechanistic and kinetic study of enzymatically initiated RAFT polymerization is performed by combining enzymatic assays and polymerization kinetics analysis. Horseradish peroxidase (HRP) initiated RAFT polymerization of dimethylacrylamide (DMAm) was studied. This polymerization was controlled by 2-(propionic acid)ylethyl trithiocarbonate (PAETC) in the presence of H₂O₂ as a substrate and acetylacetone (ACAC) as a mediator. In general, well controlled polymers with narrow molecular weight distributions and good agreement between theoretical and measured molecular weights are consistently obtained by this method. Kinetic and enzymatic assay analyses show that HRP loading accelerates the reaction, with a critical concentration of ACAC needed to effectively generate polymerization initiating radicals. The PAETC RAFT agent is required to control the reaction, although the RAFT agent also has an inhibitory effect on enzymatic performance and polymerization. Interestingly, although H₂O₂ is the substrate for HRP there is an optimal concentration near 1 mM, under the conditions studies, with higher or lower concentrations leading to lower polymerization rates and poorer enzymatic activity. This is explained through a competition between the H₂O₂ acting as a substrate, but also an inhibitor of HRP at high concentrations. Full article

There is growing interest in the use of furans, a class of alternative fuels derived from biomass, as transportation fuels. This paper reviews recent progress in the characterization of its combustion properties. It reviews their production processes, theoretical kinetic explorations and fundamental combustion properties. The theoretical efforts are focused on the mechanistic pathways for furan decomposition and oxidation, as well as the development of detailed chemical kinetic models. The experiments reviewed are mostly concerned with the temporal evolutions of homogeneous reactors and the propagation of laminar flames. The main thrust in homogeneous reactors is to determine global chemical time scales such as ignition delay times. Some studies have adopted a comparative approach to bring out reactivity differences. Chemical kinetic models with varying degrees of predictive success have been established. Experiments have revealed the relative behavior of their combustion. The growing body of literature in this area of combustion chemistry of alternative fuels shows a great potential for these fuels in terms of sustainable production and engine performance. However, these studies raise further questions regarding the chemical interactions of furans with other hydrocarbons. There are also open questions about the toxicity of the byproducts of combustion. Full article