Hydrogen Transfer Mechanism Research Articles

A comprehensive DFT-based study of the antioxidant properties of monolignols: Mechanism, kinetics, and influence of physiological environments

Monolignols, p-coumaryl alcohol (CouA), coniferyl alcohol (ConiA), and sinapyl alcohol (SinA), are the fundamental materials for lignin biosynthesis, a major component of lignocellulosic biomass. In the present study, we report a comprehensive analysis of the antioxidant properties of monolignols, using density functional theory (DFT) calculations. Under model physiological conditions, monolignols demonstrated a high hydroperoxyl radical scavenging capacity in polar media, with overall rate constants (koverall) ranging from 5.80 × 106 to 1.15 × 107 M−1 s−1. In contrast, this activity was less pronounced in lipid media, with koverall in the range of 2.66 × 102 to 2.61 × 104 M−1 s−1. The single electron transfer (SET) mechanism was found to play a decisive role in water at physiological pH and under basic conditions, whereas the formal hydrogen transfer (FHT) mechanism was the exclusive pathway in aqueous acid conditions and lipid media. Furthermore, the monolignols ConiA and SinA, demonstrated a strong capacity to chelate Cu(II) and Fe(III) ions in water, with apparent equilibrium constants in the range of 9.21 × 1014 to 5.93 × 1021 M−1 s−1. Their complexes were also found to be highly effective in blocking the reduction of Cu(II)-to-Cu(I) and Fe(III)-to-Fe(II) via the ascorbic acid anion pathway.

Heterogeneously Catalyzed Reductive Depolymerization of Lignin to Value-Added Chemicals.

Lignin is an abundant renewable source of aromatics, but its complex heterogeneous structure poses challenges for its depolymerization and valorization. Heterogeneously catalyzed reductive depolymerization (HCRD) has emerged as a promising approach, utilizing heterogeneous catalysts to facilitate selective bond cleavage in lignin and hydrogen transfer to stabilize the products under mild conditions. This review provides a comprehensive understanding of the hydrogen transfer mechanisms in HCRD, involving different hydrogen sources, including molecular hydrogen, alcohols, formic acid, etc., and the native hydrogen donor groups in lignin. The interaction between hydrogen sources and catalyst design is explored, emphasizing how catalyst characteristics must align with specific hydrogen transfer pathways to optimize efficiency and selectivity. Precious metal-based and non-precious metal-based catalysts are examined, highlighting advances that enhance hydrogen activation and transfer. Comparative analyses of hydrogen sources reveal distinct advantages and limitations. The significance of HCRD in lignin valorization and the development of integrated biorefineries is underscored, emphasizing its potential to contribute to a sustainable bioeconomy through improved process integration and economic viability.

Insights into the Synergistic Interplay of Ligand and Base Effects in Palladium-Catalyzed Enantioselectivity Hydrofunctionalization of Dienes.

Transition-metal-catalyzed enantioselective C-O bond constructions via hydrofunctionalization involving the use of O-based nucleophiles are an important topic in synthetic chemistry. Herein, density functional theory calculations were conducted to unveil the mechanism and enantioselectivity of Pd-catalyzed asymmetric hydrofunctionalization of conjugated dienes. We found that the base-assisted 4,3-activation model of the ligand-to-ligand hydrogen transfer (LLHT) mechanism is the most preferred one among all the cases, which could be ascribed to the favorable C-H···O interactions and the electrostatic interactions. For the enantioselective C-O bond formation process, the orientation of the substrate in the chiral pocket plays a significant role in controlling the enantioselectivity by contributing different noncovalent interactions. On the basis of the distortion/interaction model and energy decomposition analysis, the distortion energy is identified as the dominant factor controlling the product chemoselectivity. BnOH acts as the substrate, proton shuttle, and stabilizer to facilitate the H-transfer process in both LLHT and the C-O bond formation process. This study provides molecular-level insights into the collaborative effect of the base and P,N-ligand to perform the catalytic activity in the asymmetric hydrofunctionalization of conjugated dienes, which might open a new avenue for designing more efficient base-assisted enantioselective hydrofunctionalization by Pd catalysis.

Mechanistic Insights into the Antioxidant and Pro-oxidant Activities of Bromophenols from Marine Algae: A DFT Investigation.

Marine algae are a rich source of aromatic secondary metabolites, with bromophenols (BPs) receiving particular attention due to their health benefits. Despite extensive research on BPs, the understanding of their antioxidant potential, as well as their mechanisms of action at the molecular level, remains incomplete. This study utilized density functional theory (DFT) to systematically elucidate the antioxidant and pro-oxidant mechanisms of the main BP scaffolds under physiological conditions. It was found that BPs exhibit potent antioxidant capacity in both polar and lipid environments. In lipid media, the formal hydrogen transfer mechanism has been identified as the exclusive antiradical pathway. The position of bromine atoms significantly influenced the activity, particularly in scaffolds containing one hydroxyl group. However, no significant effect was observed in scaffolds with two hydroxyl groups. In water, monodeprotonated BPs showed key radical scavenging activity, with different mechanisms favored depending on the configuration of the hydroxyl groups. Additionally, BPs, particularly those bearing a catechol moiety, exhibit secondary antioxidant activity by reducing the production of hydroxyl radicals via the ascorbic acid anion pathway. These findings provide further validation of the potent antioxidant properties of BPs and shed light on their mechanism of action in physiological environments.

Catalytic hydroconversion of aryl ethers to polycyclic alkanes over Ni@MCM-41/β composite zeolite: Aromatic α-carbon activation and hydrogen transfer mechanisms

To produce high-density liquid fuels from lignite, a novel Ni-based bifunctional MCM-41/β composite zeolite (Ni@M/β) is reported for the catalytic hydroconversion (CHC) of lignite-derived aryl ethers to high-yield polycyclic alkanes (PCAs). Ni@M/β has a three-dimensional channel-type hierarchical porous texture with β as the core and MCM-41 as the shell. Stable Brønsted/Lewis acid sites and abundant internal/inter-zeolite defects also effectively promote the CHC of aryl ethers to PCAs. Under optimal conditions (5 MPa initial H2 pressure and 160 °C), selectivities of 2-(benzyloxy)naphthalene (BON) and benzyloxybenzene derived PCAs are as high as 76.0 and 90.5 %, respectively, with dimers and trimers dominating. DFT calculation based on electrostatic potential distribution on the van der Waals surface and Mulliken charge distribution of BON and derived oxygenated monomers shows that aromatic intermediates with >CaromaticOH have multiple accessible sites and are easy to bind with cation/radical fragments. Therefore, it is speculated that PCAs are mainly derived from C-C coupling induced by cation/radical fragments after the activation of aromatic α-carbon. In addition, the activation of H2 to H+, H·, δ+H···Hδ-, and H···H is mainly attributed to the strong Ni-M/β interaction and abundant defects. The whole CHC process is triggered mainly by the adsorption of H+ released by Ni@M/β at O sites of aryl ethers, and >Caliphatic-O- bridged bond cleavage is dominant. During this period, benzyl cation/radical produced by >C-O- bond cleavage and aromatic α-carbon activation (mainly) is coupled/reformed with adjacent aromatic fragments into corresponding polymers with non-oxygen bridged bonds, which are more easily converted to PCAs. This polycrystalline composite strategy improves the accessibility of large-sized molecules to active centers, and then increases the yields of PCAs, which is attractive for the clean and efficient conversion of lignite-derived oils to high-density liquid fuels.

Recent Understanding of Water‐Assisted CO2 Hydrogenation to Alcohols

AbstractAlcohol production from CO2 hydrogenation is a cutting‐edge process in sustainable chemistry that holds vast promise for addressing climate change by recycling and repurposing emissions. Many strategies have been proposed to improve the process efficiency. In‐situ generated, and trace amounts of water added to the feed stream have recently proved to be determinant to promote key reaction steps, increasing alcohol selectivity and yield. Here, we discuss the main findings that led to an atomic‐level understanding of water promotional effects in CO2 hydrogenation to alcohols. H2O and the products resultant from its dissociation (OH and O) can act in different ways, stabilizing intermediates and active sites or participating in the hydrogen transfer mechanisms during the reaction. Gaining insights into the mechanisms underlying water promotion offers a cost‐effective strategy for enhancing alcohol production efficiency.

Remotely Bonded Bridging Dioxygen Ligands Enhance Hydrogen Transfer in a Silica-Supported Tetrairidium Cluster Catalyst.

A longstanding challenge in catalysis by noble metals has been to understand the origin of enhancements of rates of hydrogen transfer that result from the bonding of oxygen near metal sites. We investigated structurally well-defined catalysts consisting of supported tetrairidium carbonyl clusters with single-atom (apical iridium) catalytic sites for ethylene hydrogenation. Reaction of the clusters with ethylene and H2 followed by O2 led to the onset of catalytic activity as a terminal CO ligand at each apical Ir atom was removed and bridging dioxygen ligands replaced CO ligands at neighboring (basal-plane) sites. The presence of the dioxygen ligands caused a 6-fold increase in the catalytic reaction rate, which is explained by the electron-withdrawing capability induced by the bridging dioxygen ligands, consistent with the inference that reductive elimination is rate-determining. Electronic-structure calculations demonstrate an additional role of the dioxygen ligands, changing the mechanism of hydrogen transfer from one involving equatorial hydride ligands to that involving bridging hydride ligands. This mechanism is made evident by an inverse kinetic isotope effect observed in ethylene hydrogenation reactions with H2 and, alternatively, with D2 on the cluster incorporating the dioxygen ligands and is a consequence of quasi-equilibrated hydrogen transfer in this catalyst. The same mechanism accounts for rate enhancements induced by the bridging dioxygen ligands for the catalytic reaction of H2 with D2 to give HD. We posit that the mechanism involving bridging hydride ligands facilitated by oxygen ligands remote from the catalytic site may have some generality in catalysis by oxide-supported noble metals.

Mechanistic insight into the borrowing hydrogen reaction catalysed by a Pd MLC catalyst: unveiling the ligand-to-ligand hydrogen transfer pathway

This theoretical study unveils a novel ligand-to-ligand hydrogen transfer mechanism in the borrowing hydrogen reaction.

Reaction of methylene blue with OH radicals in the aqueous environment: mechanism, kinetics, products and risk assessment.

Methylene Blue (MB) is an industrial chemical used in a broad range of applications, and hence its discharge is a concern. Yet, the environmental effects of its degradation by HO˙ radicals have not been fully studied yet. This study employs quantum chemical calculations to investigate the two-step degradation of MB by HO˙ radicals in aqueous environments. It was found that MB undergoes a rapid reaction with the HO˙ radical, with an overall rate constant of 5.51 × 109 to 2.38 × 1010 M-1 s-1 and has a rather broad lifetime range of 11.66 hours to 5.76 years in water at 273-383 K. The calculated rate constants are in good agreement with the experimental values (k calculation/k experimental = 2.62, pH > 2, 298 K) attesting to the accuracy of the calculation method. The HO˙ + MB reaction in water followed the formal hydrogen transfer and radical adduct formation mechanisms, yielding various intermediates and products. Based on standard tests these intermediates and some of the products can pose a threat to aquatic organisms, including fish, daphnia, and green algae, they have poor biodegradability and have the potential to induce developmental toxicity. Hence MB in the environment is of moderate concern depending on the ratio of safe to harmful breakdown products.

The radical scavenging activity of monocaffeoylquinic acids: the role of neighboring hydroxyl groups and pH levels.

Caffeoylquinic acids (CQAs) are well-known antioxidants. However, a key aspect of their radical scavenging activity - the mechanism of action - has not been addressed in detail thus far. Here we report on a computational study of the mechanism of activity of CQAs in scavenging hydroperoxyl radicals. In water at physiological pH, the CQAs demonstrated ≈ 104 times higher HOO˙ antiradical activity than in lipid medium (k(lipid) ≈ 104 M-1 s-1). The activity in the aqueous solution was determined by the hydrogen transfer mechanism of the adjacent hydroxyl group (O6'-H) of the dianion states (Γ = 93.2-95.2%), while the single electron transfer reaction of these species contributed 4.8-6.8% to the total rate constants. The kinetics estimated by the calculations are consistent with experimental findings in water (pH = 7.5), yielding a kcalculated/kexperimental = 2.4, reinforcing the reliability and precision of the computational method and demonstrating its utility for evaluating radical reactions in silico. The results also revealed the pH dependence of the HOO˙ scavenging activity of the CQAs; activity was comparable for all compounds below pH 3, however at higher pH values 5CQA reacted with the HOO˙ with lower activity than 3CQA or 4CQA. It was also found that CQAs are less active than Trolox below pH 4.7, however over pH 5.0 they showed higher activity than the reference. The CQAs had the best HOO˙ antiradical activity at pH values between 5.0 and 8.6. Therefore, in the physiological environment, the hydroperoxyl antiradical capacity of CQAs exhibits similarity to renowned natural antioxidants including resveratrol, ascorbic acid, and Trolox.

Unraveling Reactivity Pathways: Dihydrogen Activation and Hydrogenation of Multiple Bonds by Pyramidalized Boron-Based Frustrated Lewis Pairs.

The activation of H2 by pyramidalized boron-based frustrated Lewis Pairs (FLPs) (B/E-FLP systems where "E" refers to N, P, As, Sb, and Bi) have been explored using density functional theory (DFT) based computational study. The activation pathway for the entire process is accurately characterized through the utilization of the activation strain model (ASM) of reactivity, shedding light on the underlying physical factors governing the process. The study also explores the hydrogenation process of multiple bonds with the help of B/N-FLP. The research findings demonstrate that the liberation of activated dihydrogen occurs in a synchronized, albeit noticeably asynchronous, fashion. The transformation is extensively elucidated using the activation strain model and the energy decomposition analysis. This approach suggests a co-operative double hydrogen-transfer mechanism, where the B-H hydride triggers a nucleophilic attack on the carbon atom of the multiple bonds, succeeded by the migration of the protic N-H.

Mechanistic study of the Ni-catalyzed hydroalkylation of 1,3-dienes: The origins of regio- and enantioselectivities and a further rational design.

The development of the catalytic regio- and enantioselective hydrofunctionalization of 1,3-dienes remains a challenge and requires deep insight into the reaction mechanisms. We herein thoroughly studied the reaction mechanism of the Ni-catalyzed hydroalkylation of 1,3-dienes with ketones by density functional theory (DFT) calculations. It reveals that the reaction is initiated by stepwise oxidative addition of EtO-H followed by 1,3-diene migratory insertion to generate the alkylnickel(II) intermediate, rather than the experimentally proposed ligand-to-ligand hydrogen transfer (LLHT) mechanism. In addition, we rationalized the role of t BuOK in the subsequent addition of enolate of ketone and transmetalation process. Based on the whole catalysis, the CC reductive elimination step, turns out to be the rate- and enantioselectivity-determining step. Furthermore, we disclosed the origins of the regio- and enantioselectivity of the product, and found that the 1,2-selectivity lies in the combination effects of the ligand-substrate electrostatic interactions, orbital interactions and Pauli repulsions, while the enantioselectivity mainly arises from substrate-ligand steric repulsions. Based on mechanistic study, new biaryl bisphosphine ligands affording higher enantioselectivity were designed, which will help to improve current catalytic systems and develop new transition-metal-catalyzed hydroalkylations.

Initial Decomposition Mechanism of H2O2 at High Temperature and Pressure

In recent years, H2O2 as an excellent rocket propellant has been widely studied. Herein, the initial decomposition mechanism of H2O2 is studied in detail by molecular dynamics simulation based on density functional theory. It is found that when the energy input to H2O2 is low, the mechanism of intermolecular hydrogen transfer is dominant. With the increase of input energy, the breaking of O–O becomes the first step of the initial reaction, H–O fracture becomes the second step, and finally the transfer of hydrogen to produce H2O and HO2.

A Comprehensive Study of the Radical Scavenging Activity of Rosmarinic Acid.

Rosmarinic acid (RA) is reported in separate studies to be either an inducer or reliever of oxidative stress, and this contradiction has not been resolved. In this study, we present a comprehensive examination of the radical scavenging activity of RA using density functional theory calculations in comparison with experimental data. In model physiological media, RA exhibited strong HO• radical scavenging activity with overall rate constant values of 2.89 × 1010 and 3.86 × 109 M-1 s-1. RA is anticipated to exhibit excellent scavenging properties for HOO• in an aqueous environment (koverall = 3.18 × 108 M-1 s-1, ≈2446 times of Trolox) following the hydrogen transfer and single electron transfer pathways of the dianion state. The neutral form of the activity is equally noteworthy in a lipid environment (koverall = 3.16 × 104 M-1 s-1) by the formal hydrogen transfer mechanism of the O6(7,15,16)-H bonds. Chelation with RA may prevent Cu(II) from reduction by the ascorbic acid anion (AA-), hence blocking the OIL-1 pathway, suggesting that RA in an aqueous environment also serves as an OIL-1 antioxidant. The computational findings exhibit strong concurrence with the experimental observations, indicating that RA possesses a significant efficacy as a radical scavenger in physiological environments.

Mechanisms of chemical vapor generation by aqueous boranes for trace element analysis: a rather long and unfinished story

Abstract This paper reports a summary of the studies on the mechanisms that govern the generation of hydrides and other volatile species through reaction with aqueous boranes (CVG). This derivatization reaction has been used since the early 1970s for elemental determination and speciation from the trace level down to the ultratrace level and below. An IUPAC project, concluded in 2011, reported on the mechanisms of hydrogen transfer from borane to the analytical substrate and served to remove erroneous concepts that had dominated CVG until the early 2000s. Following the conclusion of the IUPAC project, many studies have been published on the mechanisms of CVG under conditions approaching those of analyzes of real samples. These studies included the definition of more general reaction models, which valid under non-analytical conditions, the mechanism of action of additives and interferences in CVG of volatile hydrides. In addition to the analytical utility for CVG, the results represent a contribution to the knowledge of the chemistry of aqueous boranes. Other studies will be necessary to clarify still unknown aspects, among them the identity of volatile transition metal species formed by reaction of metal ions with aqueous boranes.

The Acquisition of Primary Amines from Alcohols through Reductive Amination over Heterogeneous Catalysts

The synthesis of primary amines via the reductive amination of alcohols involves a hydrogen-borrowing or hydrogen-transfer mechanism, which consists of three main steps: alcohol hydroxyl dehydrogenation, carbonyl imidization, and imine hydrogenation. Heterogeneous catalysts are widely used for this reaction because of their high performance and amenability to separation and reuse. However, the efficiency of reductive amination is limited by the dehydrogenation step, which is severely affected by the competitive adsorption of NH3. We hope to improve the efficiency of reductive amination by increasing dehydrogenation efficiency. Therefore, in this overview, we introduce the research progress of alcohol reductive amination reaction catalyzed by heterogeneous metal catalysts, focusing on methods of enhancing dehydrogenation efficiency by screening the metal component and the acidity/alkalinity of the support. Finally, we propose some new strategies for the preparation of catalysts from the perspective of overcoming the competitive adsorption of NH3 and speculate on the design and synthesis of novel catalysts with high performance in the future.

Antiradical Activity of Lignans from Cleistanthus sumatranus: Theoretical Insights into the Mechanism, Kinetics, and Solvent Effects.

Sumatranus lignans (SL) isolated from Cleistanthus sumatranus have demonstrated bioactivities, e.g., they were shown to exhibit immunosuppressive properties in previous research. Their structure suggests potential antioxidant activity that has not attracted any attention thus far. Consistently, a comprehensive analysis of the antioxidant activity of these compounds is highly desirable with the view of prospective medical applications. In this work, the mechanism and kinetics of the antiradical properties of SL against hydroperoxyl radicals were studied by using calculations based on density functional theory (DFT). In the lipid medium, it was discovered that SL reacted with HOO• through the formal hydrogen transfer mechanism with a rate constant of 101-105 M-1 s-1, whereas in aqueous media, the activity primarily occurred through the sequential proton loss electron transfer mechanism with rate constants of 102-108 M-1 s-1. In both lipidic and aqueous environments, the antiradical activity of compounds 6 and 7 exceeds that of resveratrol, ascorbic acid, and Trolox. These substances are therefore predicted to be good radical scavengers in physiological environments.

Aquathermolysis of heavy oil using a mixed nickel-oxide/iron-oxide catalyst: Effects induced by crystal phase of iron oxide

Nickel and iron compounds have garnered attention as catalysts for upgrading heavy oil via aquathermolysis. However, research on the performance of bimetallic oxide catalysts in aquathermolysis remains limited. To that end, NiO–Fe2O3 catalysts were prepared in this study using a simple physical mixing method and employed in heavy-oil aquathermolysis to investigate the synergistic relationship between NiO and Fe2O3. The product distributions and quality were systematically analyzed, and an asphaltene upgrading index was introduced to evaluate the coke-inhibiting ability of the catalysts. Interestingly, the crystal structure of Fe2O3 in the NiO–Fe2O3 catalysts remarkably influenced the catalytic performance. Particularly, the NiO/α-Fe2O3 catalyst with highly crystalline α-Fe2O3 considerably prolonged the coke induction period up to ∼30% of residue conversion and induced a high deasphalted oil yield from asphaltenes. Moreover, NiO/α-Fe2O3 improved the product quality by removing impurities (S, N, and O) and increasing the H/C ratio. However, the liquid product distribution remained dependent on the thermal cracking effect, as the NiO–Fe2O3 catalysts did not participate in C–C cleavage. Deuterium tracing was performed to elucidate the hydrogen-transfer mechanism in catalytic aquathermolysis. The formation of deuterium–carbon single bonds from catalytic aquathermolysis was three times higher than that in the absence of the catalyst, confirming that NiO/α-Fe2O3 facilitated hydrogen transfer from water molecules to hydrocarbons during aquathermolysis.

Ni(II)-Catalyzed Transfer Hydrogenation of Azoarenes with NH3BH3.

A nickel-catalyzed semihydrogenation of azoarenes to hydrazoarenes with NH3BH3 is developed. The catalytic system exhibits good functional group tolerance and a high turnover frequency at room temperature. Results of control and deuterium-labeling experiments indicate that the ethanol hydroxyl and BH3 groups each donated one hydrogen to this transfer hydrogenation, and the main byproducts were B(OEt)3 and H2. Moreover, density functional theory calculations indicated that the reaction proceeded via a ligand-to-ligand hydrogen transfer mechanism. This study presents a novel nickel catalytic system for the semihydrogenation of azoarenes.

Hydrogen Radical-Induced Electrocatalytic N2 Reduction at a Low Potential.

Realizing efficient hydrogenation of N2 molecules in the electrocatalytic nitrogen reduction reaction (NRR) is crucial in achieving high activity at a low potential because it theoretically requires a higher equilibrium potential than other steps. Analogous to metal hydride complexes for N2 reduction, achieving this step by chemical hydrogenation can weaken the potential dependence of the initial hydrogenation process. However, this strategy is rarely reported in the electrocatalytic NRR, and the catalytic mechanism remains ambiguous and lacks experimental evidence. Here, we show a highly efficient electrocatalyst (ruthenium single atoms anchored on graphdiyne/graphene sandwich structures) with a hydrogen radical-transferring mechanism, in which graphdiyne (GDY) generates hydrogen radicals (H•), which can effectively activate N2 to generate NNH radicals (•NNH). A dual-active site is constructed to suppress competing hydrogen evolution, where hydrogen preferentially adsorbs on GDY and Ru single atoms serve as the adsorption site of •NNH to promote further hydrogenation of NH3 synthesis. As a result, high activity and selectivity are obtained simultaneously at -0.1 V versus a reversible hydrogen electrode. Our findings illustrate a novel hydrogen transfer mechanism that can greatly reduce the potential and maintain the high activity and selectivity in NRR and provide powerful guidelines for the design concept of electrocatalysts.