Orientation Of Reactants Research Articles

Computational Study of the 1,3-Dipolar Cycloaddition between Criegee Intermediates and Linalool: Atmospheric Implications.

In this research, we investigated the essential role of biogenic volatile organic compound emissions in regulating tropospheric ozone levels, atmospheric chemistry, and climate dynamics. We explored linalool ozonolysis and secondary organic aerosol formation mechanisms, providing key insights into atmospheric processes. Computational techniques, such as density functional theory calculations and molecular dynamics simulations, were employed for the analysis. Our study delves into the energetic and mechanistic aspects of the 1,3-dipolar cycloadditions involving linalool and its ozonolysis byproducts, known as Criegee intermediates. A total of 24 reactions were analyzed from the three possible Criegee intermediates formed, resulting from different reactant orientations and their endo/exo isomers. We found that only four of these reactions exhibit large rate constants that can compete with tropospheric reactions. This reactivity pattern was characterized by analyzing reactivity indices from conceptual density functional theory and determining that electron flux originates from linalool to the Criegee intermediates. Greater electrophilicity in the Criegee intermediates results in a lower reaction activation energy, confirmed by the global electrophilicity index. Furthermore, using the activation strain model and energy decomposition analysis, we found that differences in activation energies were primarily driven by nonorbital energy factors. Finally, molecular dynamics simulations showed that the final cycloaddition adducts of the most favorable 1,3-dipolar cycloaddition interact favorably with water molecules in an exergonic process, adsorbing up to 92% of the water molecules after 20 ns. Our findings provide insights that enhance our understanding of the interactions between natural emissions and atmospheric constituents.

Reticulating Crystalline Porous Materials for Asymmetric Heterogeneous Catalysis

AbstractAsymmetric catalysis is essential for addressing the increasing demand for enantiopure compounds. Recent advances in reticular chemistry have demonstrated that metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) possess highly regular porous architectures, exceptional tunability, and the ability to incorporate chiral functionalities through their open channels or cavities. These characteristics make them highly effective and enantioselective catalysts for a wide range of asymmetric transformations. The chiral microenvironments within these frameworks facilitate precise control over reactant orientation and transition states, enhancing both catalytic activity and enantioselectivity, thereby offering significant advantages over traditional systems. This review overviews recent developments in chiral MOFs (CMOFs) and chiral COFs (CCOFs), focusing on their design strategies, and synthetic methods, and highlights the structure–property relationships that connect key structural features to asymmetric catalytic performance. Additionally, the current challenges and future prospects in this field are addressed, highlighting the pivotal role of reticular chemistry in the creation of chiral porous materials. It is anticipated that this review will inspire further research into the application of crystalline porous materials in asymmetric catalysis and promote the rational design of novel chiral heterogeneous catalysts for industrial use.

Self‐promoted Controlled Ring‐opening Polymerization via Side Chain‐mediated Proton Transfer for the Synthesis of Tertiary Amine‐pendant Polypeptoids

AbstractProton transfer is essential in virtually all biochemical processes, with enzymes facilitating this transfer by optimizing the proximity and orientation of reactants through site‐specific hydrogen bonds. Proton transfer is also crucial in the rate‐determining step for the ring‐opening polymerization of N‐carboxyanhydrides (NCAs), widely used to prepare various peptidomimetic materials. This study utilizes side chain‐assisted strategy to accelerate the rate of chain propagation by using NCAs with tertiary amine pendants. This moiety enables hydrogen bond formation between the incoming NCA and the polymer amino growing end. The tertiary amine side chain of the NCA forms a proton shuttle, via a less constrained transition state, to facilitate the proton transfer process. Moreover, the tertiary amine side chains enable the precipitation of NCA monomers through in situ protonation during the monomer synthesis. This greatly facilitates the synthesis of these unreported monomers, allowing the direct controlled synthesis of tertiary amine‐pendant polypeptoids. This side chain‐promoted polymerization has rarely been reported. Additionally, the tertiary amine side chains, as widely used functional groups, endow the polymers with unique properties including pH‐ and thermo‐responsiveness, tunable pKas, and siRNA transfection capability. The self‐promoted synthesis, facile monomer preparation, and attractive properties make tertiary amine‐pendant polypeptoids promising materials for various applications.

Self-promoted Controlled Ring-opening Polymerization via Side Chain-mediated Proton Transfer for the Synthesis of Tertiary Amine-pendant Polypeptoids.

Proton transfer is essential in virtually all biochemical processes, with enzymes facilitating this transfer by optimizing the proximity and orientation of reactants through site-specific hydrogen bonds. Proton transfer is also crucial in the rate-determining step for the ring-opening polymerization of N-carboxyanhydrides (NCAs), widely used to prepare various peptidomimetic materials. This study utilizes side chain-assisted strategy to accelerate the rate of chain propagation by using NCAs with tertiary amine pendants. This moiety enables hydrogen bond formation between the incoming NCA and the polymer amino growing end. The tertiary amine side chain of the NCA forms a proton shuttle, via a less constrained transition state, to facilitate the proton transfer process. Moreover, the tertiary amine side chains enable the precipitation of NCA monomers through in situ protonation during the monomer synthesis. This greatly facilitates the synthesis of these unreported monomers, allowing the direct controlled synthesis of tertiary amine-pendant polypeptoids. This side chain-promoted polymerization has rarely been reported. Additionally, the tertiary amine side chains, as widely used functional groups, endow the polymers with unique properties including pH- and thermo-responsiveness, tunable pKas, and siRNA transfection capability. The self-promoted synthesis, facile monomer preparation, and attractive properties make tertiary amine-pendant polypeptoids promising materials for various applications.

Evaluating the Ability of External Electric Fields to Accelerate Reactions in Solution.

This study investigates the catalytic effects of external electric fields (EEFs) on two reactions in solution: the Menshutkin reaction and the Chapman rearrangement. Utilizing a scanning tunneling microscope-based break-junction (STM-BJ) setup and monitoring reaction rates through high-performance liquid chromatography connected to a UV detector (HPLC-UV) and ultraperformance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-q-ToF-MS), we observed no rate enhancement for either reaction under ambient conditions. Density functional theory (DFT) calculations indicate that electric field-induced changes in reactant orientation and the minimization of activation energy are crucial factors in determining the efficacy of EEF-driven catalysis. Our findings suggest that the current experimental setups and field strengths are insufficient to catalyze these reactions, underscoring the importance of these criteria in assessing the reaction candidates.

Synergistic Effect of Single‐Atom Catalysts and Vacancies of Support for Versatile Catalytic Applications

AbstractThe combination of single‐atom catalysts and vacancy engineering is an emerging hotspot in the field of single‐atom catalysis. The existence of vacancies provides additional adsorption sites, which can increase the adsorption capacity and diffusion rate of reactant molecules. Single atoms have single‐height atom utilization and steric hindrance effects. The two synergistically show different activation and synergistic processes on different defect materials. Under the synergistic effect of vacancies and single‐atom catalysts, they can affect the adsorption orientation of reactants on the catalyst surface and the formation of intermediate configurations, thereby regulating the reaction path and product selectivity, greatly enhancing the catalytic performance, and maximizing the catalytic effect of the material itself. Therefore, the synergistic effect between pervacancies and single‐atom catalysts can realize more efficient, sustainable, and economical catalytic reaction systems, possessing high‐efficiency performance in photocatalysis, electrocatalysis and thermocatalysis, and setting off a new wave in the fields of energy conversion, environmental protection, and organic synthesis. Therefore, catalysts constructed by vacancies and single atoms have broad and bright application prospects.

Quantum stereodynamics studies for the Li + HF (v = 0, j = 1) → H + LiF reaction

In reactive collisions, the colliding direction has an important effect on the reaction dynamics, and the study of reaction stereodynamics which controls the initial orientation or alignment of reactants is of great significance for controlling chemical reactions. In this work, the influence of different initial reactant orientations on the Li + HF (v0 = 0, j0 = 1) → LiF + H reaction dynamics are studied by using the quantum wave packet method. We found that the initial orientation of HF molecule has a great influence on the reactivity and scattering direction of product, but has little influence on the product rotational-vibrational state distribution.

Directing Reaction Pathways on Supported Metal Catalysts with Low-Density Self-Assembled Monolayers

Controlling reactant adsorption on catalyst surfaces is crucial to reaction activity and selectivity. One method for improving selectivity is by imposing steric constraints to bias the reactant binding orientation. In this study, thiol self-assembled monolayers (SAMs) were deposited onto Pt/Al2O3 catalysts as a method for controlling activity and selectivity via steric effects. In addition to a full monolayer, a low-density SAM-coated catalyst was employed. A number of characterization techniques demonstrated the successful deposition of homogeneous low-density SAMs on the metal surface with reduced site-blocking compared to a full high-density monolayer. Reaction kinetic studies showed increased benzyl alcohol hydrodeoxygenation (HDO) selectivity for both SAM-modified catalysts. This was attributed to the inability of the reactant to adsorb on the catalyst with the aromatic ring parallel to the surface, thus preventing decarbonylation and ring hydrogenation reaction pathways. Additionally, SAM density influenced reaction activity significantly, with the low-density-modified SAM catalyst being more active than the catalyst coated with a full monolayer. Moreover, liquid-phase hydrogenation reactions were used to investigate the relationship between SAM density and reactivity for reactant molecules of various sizes. In all cases, the low-density SAM improved reaction rates relative to dense SAMs. The effect of controlling ligand density depended on the type of reaction: high ligand densities greatly diminished ring hydrogenation, while HDO was largely unaffected, suggesting a potential strategy for size-selective reaction rate and selectivity control.

Probing Copper and Copper-Gold Alloy Surfaces with Space-Quantized Oxygen Molecular Beam.

The orientation and motion of reactants play important roles in reactions. The small rotational excitations involved render the reactants susceptible to dynamical steering, making direct comparison between experiments and theory rather challenging. Using space-quantized molecular beams, we directly probed the (polar and azimuthal) orientation dependence of O2 chemisorption on Cu(110) and Cu3Au(110). We observed polar and azimuthal anisotropies on both surfaces. Chemisorption proceeded rather favorably with the O–O bond axis oriented parallel (vs perpendicular) to the surface and rather favorably with the O–O bond axis oriented along [001] (vs along [1̅10]). The presence of Au hindered the surface from further oxidation, introducing a higher activation barrier to chemisorption and rendering an almost negligible azimuthal anisotropy. The presence of Au also prevented the cartwheel-like rotations of O2.

Controlling the Spin-Orbit Branching Fraction in Molecular Collisions.

The collision geometry, that is, the relative orientation of reactants before interaction, can have a large effect on how a collision or reaction proceeds. Certain geometries may prevent access to a given product channel, while others might enhance it. In this Letter, we demonstrate how the initial orientation of NO molecules relative to approaching Ar atoms determines the branching between the spin-orbit changing and the spin-orbit conserving rotational product channels. We use a recently developed quantum treatment to calculate differential and integral branching fractions, at any arbitrary orientation, from theoretical and experimental data points. Our results show that a substantial degree of control over the final spin-orbit state of the scattering products can be achieved by tuning the initial collision geometry.

Reaction Dynamics of Cyanohydrins with Hydrosulfide in Water.

We studied the reaction dynamics of a proposed prebiotic reaction theoretically. The chemical process involves acetone cyanohydrin or formalcyanohydrin reacting with hydrosulfide in an aqueous environment. Rate constants and populations of reactant and product bimolecular geometric orientations for the reactions were obtained by using density functional theory for the energies, transition-state theory for the rates, and matrix exponentiation as well as the hybrid tau-leaping algorithm for the population dynamics. The role of including the solvent explicitly versus implicitly was also investigated. We found that adding explicit water or hydrogen sulfide molecules lowers the activation energy barrier and leads to a more efficient reaction pathway. In particular, hydrogen sulfide was a better proton donor. Finally, we studied the role of including more than one reactant and product bimolecular orientation geometry in the dynamics. Including all initial pathways, reactant to reactant, product to product, reactant to product, and product to reactant led to a larger reaction rate constant compared to the single minimum energy pathway approach. Overall, we found that most reactions which involve formalcyanohydrin occur more rapidly or at the same speed as reactions which involve acetone cyanohydrin at room temperature.

A Reaction Valley Investigation of the Cycloaddition of 1,3-Dipoles with the Dipolarophiles Ethene and Acetylene: Solution of a Mechanistic Puzzle.

The reaction mechanism of the cycloaddition of 10 1,3-dipoles with the two dipolarphiles ethene and acetylene is investigated and compared using the Unified Reaction Valley Approach in a new form, which is based on a dual-level strategy, an accurate description of the reaction valley far out into the van der Waals region, and a comparative analysis of the electronic properties of the reaction complex. A detailed one-to-one comparison of 20 different 1,3-dipolar cycloadditions is performed, and unknown mechanistic features are revealed. There are significant differences in the reaction mechanisms for the two dipolarophiles that result from the van der Waals complex formation in the entrance channel of the cycloadditions. Hydrogen bonding between the 1,3-dipoles and acetylene is generally stronger, which leads to higher reaction barriers in the acetylene case, but which also facilitates to overcome the problem of a reduced charge transfer from 1,3-dipole to acetylene. Mechanistic differences are found in the prechemical and chemical reaction regions with regard to reactant orientation, preparation for the reaction, charge transfer, charge polarization, rehybridization, and bond formation. It is shown that similarities in the reaction barriers as determined by CCSD(T)-F12/aug-cc-pVTZ calculations result from a fortuitous cancellation of different electronic effects. In general, a caveat must be made with regard to oversimplified descriptions of the reaction mechanism based on orbital theory or energy decomposition schemes.

Origin of Steric Effects in Methane Dissociative Chemisorption

Steric effects in chemical reactions, namely, the dependence of reactivity on reactant spatial orientation and/or alignment, provide valuable information on the anisotropic potential energy surface and access to the transition state. However, a theoretical interpretation of steric effect is often not straightforward because of convolution of the dynamics by many other factors. Here, we present a theoretical study on the dissociative chemisorption of methane using a quasi-classical trajectory method on a density functional theory based global potential energy surface and offer a theoretical interpretation of the interesting but surprising steric effect in this prototypical and industrially relevant gas–surface reaction.

A new perspective: imaging the stereochemistry of molecular collisions.

The concept of the steric effect in molecular collisions is central to chemistry. In this Perspective article we review some of the progress made in studying the steric effect in inelastic and reactive collisions involving relatively small isolated atomic and molecular species. We overview the theoretical framework used to quantify the steric effect, and outline some of the key experimental approaches that can be employed to study the dynamics and mechanism of collisions involving oriented and aligned molecules. We illustrate the discussion by highlighting a few recent studies of inelastic and reactive scattering. Finally, we conclude with some reflections on possible future directions of interest.

Frontispiece: Controlling an Electron-Transfer Reaction at a Metal Surface by Manipulating Reactant Motion and Orientation

Frontispiece: Controlling an Electron-Transfer Reaction at a Metal Surface by Manipulating Reactant Motion and Orientation

Preparation of gold nanostars and their study in selective catalytic reactions

Abstract In this work, gold nanostars (AuNSs) with size around 90 nm were prepared through an easy one-step method. They show excellent catalytic activity and large surface-enhanced Raman scattering (SERS) activity at the same time. Surprisingly, they exhibited different catalytic performance on the reduction of aromatic nitro compounds with different substituents on the para position. To understand such a difference, the SERS spectra were recorded, showing that the molecular orientation of reactants on the gold surface were different. We anticipate that this research will help to understand the relationship of the molecular orientation with the catalytic activity of gold nanoparticles.

Controlling an electron-transfer reaction at a metal surface by manipulating reactant motion and orientation.

The loss or gain of vibrational energy in collisions of an NO molecule with the surface of a gold single crystal proceeds by electron transfer. With the advent of new optical pumping and orientation methods, we can now control all molecular degrees of freedom important to this electron-transfer-mediated process, providing the most detailed look yet into the inner workings of an electron-transfer reaction and showing how to control its outcome. We find the probability of electron transfer increases with increasing translational and vibrational energy as well as with proper orientation of the reactant. However, as the vibrational energy increases, translational excitation becomes unimportant and proper orientation becomes less critical. One can understand the interplay of all three control parameters from simple model potentials.

ChemInform Abstract: Mesoscale Nanostructures as a Bridge Between Homogeneous and Heterogeneous Catalysis

AbstractReview: 57 refs.

Mesoscale Nanostructures as a Bridge Between Homogeneous and Heterogeneous Catalysis

The environment that surrounds catalytically active metallic nanoclusters has an important role in tuning their catalytic reactivity and selectivity and can initiate novel reaction routes. In this review we will demonstrate two different approaches for utilization of the environment in bi-functional, mesoscale catalysts. In these catalytic systems, the molecules that surround the metallic nanoclusters have an active role as co-catalysts. In the first bi-functional system, the steric effects of metal-adsorbed ligands have been exploited for regulating the adsorption orientation of reactants. By favoring specific orientation of the reactants, the products selectivity was widely tuned. In the second bi-functional catalytic system, the catalytic properties of the metallic nanoclusters were controlled by their encapsulation within a polymeric matrix. The oxidation state, catalytic reactivity and stability of metallic nanoclusters were tuned by their encapsulation in polyamidoamine dendrimer molecules. Oxidation of dendrimer-encapsulated nanoclusters into highly oxidized metal-ions activated the catalyst toward a variety of reactions which were previously catalyzed by homogeneous catalysts. Moreover, by modifying the properties of the polymeric matrix, enhanced chemo-, diastereo- and enantio-selectivity were obtained. These two examples of mesoscale catalysts indicate the important role of the surrounding environment in tuning the catalytic reactivity and selectivity. In addition, it is demonstrated that these catalysts can function as a bridge between homogeneous and heterogeneous catalysis.

RETRACTED ARTICLE: Quantum effects on translation and rotation of molecular chlorine in solid para-hydrogen

Structure and quantum effects of a Cl2 molecule embedded in fcc and hcp para-hydrogen (pH2) crystals are investigated in the zero-temperature limit. The interaction is modelled in terms of Cl2–pH2 and pH2–pH2 pair potentials from ab initio CCSD(T) and MP2 calculations. Translational and rotational motions of the molecules are described within three-dimensional anharmonic Einstein and Devonshire models, respectively, where the crystals are either treated as rigid or allowed to relax. The pH2 molecules, as well as the heavier Cl2 molecule, show large translational zero-point energies (ZPEs) and undergo large-amplitude translational motions. This gives rise to substantial reductions in the cohesive energies and expansions of the lattices, in agreement with experimental results for pure hydrogen crystals. The rotational dynamics of the Cl2 impurity is restricted to small-amplitude librations, again with high librational ZPEs, which are described in terms of two-dimensional non-degenerate anharmonic oscillators. The lattice relaxation causes qualitative changes of the rotational energy surfaces, which finally favour librations around the crystallographic directions pointing towards the nearest neighbours, both for fcc and hcp lattices. Implications on the reactant orientation in the experimentally observed laser-induced chemical reaction, Cl + H2 → HCl + H, are discussed.