MXenes with ordered triatomic-layer borate polyanion terminations.

Surface terminations profoundly influence the intrinsic properties of MXenes, but existing terminations are limited to monoatomic layers or simple groups, showing disordered arrangements and inferior stability. Here we present the synthesis of MXenes with triatomic-layer borate polyanion terminations (OBO terminations) through a flux-assisted eutectic molten etching approach. During the synthesis, Lewis acidic salts act as the etching agent to obtain the MXene backbone, while borax generates BO2- species, which cap the MXene surface with an O-B-O configuration. In contrast to conventional chlorine/oxygen-terminated Nb2C with localized charge transport, OBO-terminated Nb2C features band transport described by the Drude model, exhibiting a 15-fold increase in electrical conductivity and a 10-fold improvement in charge mobility at the d.c. limit. This transition is attributed to surface ordering that effectively mitigates charge carrier backscattering and trapping. Additionally, OBO terminations provide Ti3C2 MXene with substantially enriched Li+-hosting sites and thereby a large charge-storage capacity of 420 mAh g-1. Our findings illustrate the potential of intricate termination configurations in MXenes and their applications for (opto)electronics and energy storage.

Performance improvement of underwater LIBS qualitative and quantitative analysis by irradiating with long nanosecond pulses.

Long nanosecond pulses have been proven to be efficient at enhancing underwater LIBS emission. However, the quantitative analytical capability of underwater long-pulse LIBS has yet to be further revealed. In this work, we investigated the spectral characteristics by irradiating with a laser pulse of 120 ns duration. The alkali and alkaline earth metals Li, K and Ca and the transition element Mn were selected for analysis. It is shown that obvious self-reversal structures were observed in the spectra at high concentrations, making the calibration curves saturated. Correction was performed using the approximate Voigt function fitting method, which significantly improves the linearity of the calibration curves. In addition to the target metal elements, atomic lines of the matrix elements H and O in water were also observed, which can serve as promising internal standards for quantitative analysis. A comparison of the quantification performance with and without the internal standards demonstrates that the use of the internal standards is conducive to improving the robustness of the calibration approaches with higher determination coefficients. More importantly, the underwater LIBS signal stability is improved by more than 3 times, and the prediction error for validation samples is reduced by 2-4 times. The present results suggest that long ns pulses are favorable to significantly improving the qualitative and quantitative performance of underwater single-pulse LIBS, enabling long-pulse LIBS to have great potential to be applied to underwater in situ chemical analysis.

Robust Superamphiphobic Coating Applied to Grease-Proof Mining Transformer Components.

The iron core and heat sink in a mining transformer are susceptible to damage from oil spills or the harsh mine environment; the deterioration of oil products in the underground environment and transformers produce massive amounts of harmful liquid substances, which may lead to unnecessary economic losses in drilling engineering. To overcome this issue, a convenient and economical way to protect transformer components was developed. Herein, we proposed an air spray technology at room temperature for the preparation of antigreasy superamphiphobic coatings, which are suitable for bulk metallic glass transformer cores and ST13 heat sinks. The addition of polypyrrole powder effectively improves the thermal conductivity and specific heat of the coating in the range of 50-70 °C. More importantly, the fabricated coating has excellent repellency to liquids, such as water, ethylene glycerol, hexadecane, and rapeseed oil. Meanwhile, the coating has excellent physical and chemical resistance and outstanding antifouling features, which provide a feasible solution for combating grease pollution and corrosion in the mine environment. Taking multifaceted stability into consideration, this work contributes to enhancing the application of superamphiphobic coatings in the fields of protecting transformer components in the harsh environment or during transformer operation faults.

Robust Janus Superwetting Textile with Large Pore Sizes for Oil-in-Water Emulsion Separation.

Developing advanced oil-water separation technology is significant for environmental conservation. According to the synergetic effects of the size-sieving mechanism, superwetting materials with small pore sizes have been designed to realize high-efficiency separation for oil-water emulsions. However, the separation flux limited by the pore size and the weakness of the superwetting material impede its practical application severely. Herein, we construct a robust Janus superwetting textile with large pore sizes for oil-in-water emulsion separation. The pristine textile is coated by the as-prepared CuO nanoparticles as the bottom layer with superhydrophilicity and then grafted by 1-octadecanethiol as the top layer with superhydrophobicity to construct the Janus textile. When used as a filter, the superhydrophobic layer acts as the nucleation site to coalesce the small oil droplets facilely. Then, the coalesced oil fills the pores of the superhydrophobic layer and selectively permeates it but is blocked by the superhydrophilic layer with large pore sizes. Utilizing the unique separation mechanism, the Janus textile realizes efficient and rapid separation. Even after multicycle separation, hot liquid immersion for 24 h, tribological test for 60 min, and sandpaper abrasion for 500 cycles, the Janus textile still retains the superwettability and excellent separation performance, manifesting outstanding stability to resist severe damage. This separation strategy provides a novel guideline for high-efficiency and high-flux emulsion separation and practical application.

Competitive dynamics of E2 and SN2 reaction driven by collision energy and leaving group.

The competition between E2 and SN2 reactions is essential in organic chemistry. In this paper, the reaction mechanism of F- + CH3CH2Cl is investigated utilizing direct dynamics simulations, and unravel how the collision energy (Ecoll) and the leaving group affect the competition between SN2 and E2 in the F- + CH3CH2Y (Y = Cl and Br) reactions. Simulation results for F- + CH3CH2Cl reaction show that the anti-E2 channel is dominant, but with the increase of Ecoll from 0.04 to 1.9 eV the branching ratio of the anti-E2 pathway significantly decreases by 21%, and the SN2 pathway becomes more important. A transition from indirect to direct reaction has been revealed when Ecoll is increased from 0.04 to 1.90 eV. At lower Ecoll, a large ratio of indirect events occurs via a long-lived hydrogen-bonded complex, and as the collision energy is increased, the lifetimes of the hydrogen-bonded complexes are shortened, due to an initial faster relative velocity. The simulation results of F- + CH3CH2Cl are further compared with the F- + CH3CH2Br reaction at Ecoll of 0.04 eV. Changing the leaving group from Cl to Br drastically suppresses the indirect events of anti-E2 with a branching ratio decreasing from 0.46 to 0.36 due to the mass effect, and promotes direct rebound mechanism resulting from a looser transition state geometry caused by varied electronegativity.

Nucleophile Effects on the E2/SN2 Competition for the X- + CH3CH2Cl Reactions: A Theoretical Study.

The effect of nucleophiles on the gas-phase E2/SN2 competition is still not completely elucidated, despite its importance in chemistry. In the current work, the electronic structure calculations of prototypical reactions X- + CH3CH2Cl (X = OH, F, Cl, Br, and I) are performed at the MP2 level with aug-cc-pVDZ or ECP/d. The effects of nucleophiles on the competing E2 and SN2 reactions in terms of the correlation between the barrier height and reaction energy, electronegativity of X, bond length, charge distribution, and proton affinity of anionic nucleophile X- are explored and emphasized. As the nucleophile changes from OH- to I-, both SN2 and E2 reactions become more exothermic, with the reaction energy in the ranges from -51.9 to 10.8 kcal mol-1 (SN2) and -36.8 to 38.0 kcal mol-1(E2). For X- = F- and OH-, the sequence of reactivity for the four pathways is ret-SN2 < syn-E2 < anti-E2 ∼ inv-SN2. However, for X- = Cl-, Br-, and I-, the anti-E2 barrier is much higher in energy (17.1-29.4 kcal mol-1) than that of inv-SN2. Energy decomposition analysis illustrates that the anti-E2 pathway possesses the highly destabilizing characteristic distortion, resulting in a larger reaction barrier and hence becoming a more unfavorable pathway than inv-SN2. More interestingly, only ion-dipole complex exists in the entrance channel for reactions involving OH-, Cl-, Br-, and I-, and in contrast, a significant hydrogen-bonded complex formation is also revealed for X- = F-, which can further affect E2/SN2 competition and atomic-level mechanisms, especially, for the isoelectronic nucleophile F- and OH-. It has been revealed here that electronegativity of central atoms in X and ionic radii of nucleophiles are the important factors affecting the entrance channel complex.

Anti-rheumatoid arthritis effects of Xanthii Fructus by affecting the PI3K-AKT signaling pathway based on TMT-labeled quantitative proteomics.

Rheumatoid arthritis is a systemic autoimmune disease characterized by chronic symmetrical multiple arthritis. Current traditional counter-therapies are expensive and have side effects. Xanthii Fructus has effects in expelling wind and cold, draining the nasal orifice, and removing wind and dampness. However, its mechanism of action against rheumatoid arthritis is unknown. In this paper, the mechanism of the anti- rheumatoid arthritis effect of Xanthii Fructus is studied by proteomics. The experimental results show that it could significantly reduce serum inflammatory factor levels, alleviate joint edema, improve vasodilation and congestion, and significantly reduce the number of inflammatory cells. Proteomics results show that the PI3K-AKT signaling pathway is the key pathway for Xanthii Fructus to treat rheumatoid arthritis. In this study, we obtained a new understanding of the mechanism of Xanthii Fructus in the treatment of rheumatoid arthritis, which provided a theoretical basis for its prevention and treatment and laid the foundation for further research.

Band Structure Engineering within Two-Dimensional Borocarbonitride Nanosheets for Surface-Enhanced Raman Scattering.

Herein, with two-dimensional (2D) borocarbonitride (BCN) as a metal- and plasmon-free surface-enhanced Raman scattering (SERS) platform, we demonstrate a band structure engineering strategy to facilitate the charge transfer process for an enhanced SERS response. Especially, when the conduction band of the BCN substrate is tuned to align with the LUMO of the target molecule, remarkable SERS performance is achieved, ascribed to the borrowing effect from the vibronic coupling of resonances through the Herzberg-Teller coupling term. Meanwhile, fluorescence quenching is achieved due to the efficient charge transfer between the BCN substrate and target molecule. Consequently, BCN can accurately detect 20 kinds of trace chemical and bioactive analytes. Moreover, BCN exhibits excellent thermal and chemical stability, which can not only withstand high-temperature (300 °C) heating in the air but also resist long-term corrosion in harsh acid (pH = 0, HCl) and base (pH = 14, NaOH). This work provides new insight into band structure engineering in promoting the SERS performance of plasmon- and metal-free semiconductor substrates.

Effects of Methyl Substitution and Leaving Group on E2/SN2 Competition for Reactions of F- with RY (R = CH3, C2H5, iC3H7, tC4H9; Y = Cl, I).

The competition between base-induced elimination (E2) and bimolecular nucleophilic substitution (SN2) is of significant importance in organic chemistry and is influenced by many factors. The electronic structure calculations for the gas-phase reactions of F- + RY (R = CH3, C2H5, iC3H7, tC4H9, and Y = Cl, I) are executed at the MP2 level with aug-cc-pVDZ or ECP/d basis set to investigate the α-methyl substitution effect. The variation in barrier height, reaction enthalpy, and competition of SN2/E2 as a function of methyl-substitution and leaving group ability has been emphasized. And the nature of these rules has been explored. As the degree of methyl substitution on α-carbon increases, the E2 channel becomes more competitive and dominant with R varying from C2H5, iC3H7, to tC4H9. Energy decomposition analysis offers new insights into the competition between E2 and SN2 processes, which suggests that the drop in interaction energy with an increasing degree of substitution cannot compensate for the rapid growth of preparation energy, leading to a rapid increase in the SN2 energy barrier. By altering the leaving group from Cl to I, the barriers of both SN2 and E2 monotonically decrease, and, with the increased number of substituents, they reduce more dramatically, which is attributed to the looser transition state structures with the stronger leaving group ability. Interestingly, ∆E0‡ exhibits a positive linear correlation with reaction enthalpy (∆H) and halogen electronegativity. With the added number of substituents, the differences in ∆E0‡ and ∆H between Y = Cl and I likewise exhibit good linearity.

Functional Regulation of ZnAl-LDHs and Mechanism of Photocatalytic Reduction of CO2: A DFT Study.

Defect engineering and heteroatom doping can significantly enhance the activity of zinc-aluminum layered double hydroxides (ZnAl-LDHs) in photocatalytic CO2 reduction to fuel. However, the in-depth understanding of the associated intrinsic mechanisms is limited. Herein, we systematically investigated Zn vacancies (VZn), oxygen vacancies (VO), and Cu doping on the geometry and electronic structure of ZnAl-LDH using density functional theory (DFT). We also revealed the related reaction mechanism. The results reveal the concerted roles of VO, VZn, and doped-Cu facilitate the formation of the unsaturated metal complexes (Znδ+-VO and Cuδ+-VO). They can localize the charge density distribution, function as new active centers, and form the intermediate band. Simultaneously, the intermediate band of functionalized ZnAl-LDHs narrows the band gap and lowers the band edge location. Therefore, it can broaden the absorption range of light and improve the selectivity of CO. Additionally, the unsaturated metal complex lowers the Gibbs free energy barrier for effective CO2 activation by bringing the d-band center level closer to the Fermi level. The work provided guidance for developing LDH photocatalysts with high activity and selectivity.

Multistage Electron Distribution Engineering of Iridium Oxide by Codoping W and Sn for Enhanced Acidic Water Oxidation Electrocatalysis.

Developing efficient and robust anodic electrocatalysts to implement the proton-exchange membrane (PEM) electrolyzer is critical for hydrogen generation. Nevertheless, the only known applicable anode catalyst IrOx in PEM electrolyzers still requires high overpotential due to the weak binding energy between oxygen intermediates and active sites, limiting its wide applications. Herein, a ternary Ir0.7 W0.2 Sn0.1 Ox nanocatalyst synthesized through a sol-gel strategy, exhibits a low overpotential of 236 mV (10 mA cm-2 geo ) for thoxygen evolution reaction (OER), accompanied with robust durability over 220 h at 1 A cm-2 geo in 0.5 m H2 SO4 . Moreover, the optimized Ir0.7 W0.2 Sn0.1 Ox delivers a prominent mass activity of 722.7 A g-1 Ir at 1.53 V (vs RHE), which is around 34 times higher compared with that of IrOx . The mircrostructural analyses reveal that codoping of W and Sn stabilizes Ir with a valence state lower than 4+ through multistage charge redistribution, avoiding the overoxidation of Ir above 1.6 V versus RHE and enhancing the acidic OER performance. Additionally, density functional theory calculations reveal that codoping of W and Sn moves the d band center of Ir to the Fermi level, thus enhancing the binding energies of oxygen intermediates with Ir sites and decreasing the energy barrier toward acidic OER.

Asymmetric Robust Superhydrophobic/Superhydrophilic Janus Membranes for the Moisture Proofing of Oil and Purification of Water.

The performance degradation of oil caused by moisture and water pollution induced by the infiltration of oil can result in huge losses for society. This is especially true of stable emulsified mixtures of oil and water, which are difficult to separate and urgently require a processing method. In this work, a robust Janus membrane prepared by combining simple electrodeposition and spraying processes was used to separate water-in-transformer oil/lubricating oil emulsions and various oil-in-water emulsions. The membrane with outstanding separation efficiency was also endowed high flux to emulsions, even after 10 separation cycles and 100 sand impact tests, indicating that separation ability was retained. Furthermore, the excellent resistance to acidic and alkaline liquids of the superhydrophobic side groups of the membrane increased the possibility of its service in harsh environments. This study's findings reveal great potential regarding the expansion and application of oil-water separation materials.

Durable 3D Porous Superhydrophobic Composites for Versatile Emulsion Separation in Multiple Environments.

Polydopamine as a multifunctional biomimetic polymer with nonselective strong adhesion properties has become a hot research topic in recent years. However, there are a few reports on the durable and effective emulsion separation of polydopamine composites from other materials. Therefore, it is necessary to construct durable polydopamine composites to achieve selective adsorption of materials. In this work, polypyrrole (PPy)-PDA was obtained on sponges by an in situ polymerization reaction, followed by the attachment of SiO2 nanoparticles to the surface by polydimethylsiloxane to achieve superhydrophobicity. As a result, previously unreported selective superhydrophobic adsorbents for PPy-PDA coatings were obtained. The prepared sponges have an excellent adsorption capacity for oils and organic solvents. Not only can the sponges absorb 19-39 g of organic solvents per gram but they can also absorb oil from oil-in-water emulsions. The chemical oxygen demand value of the emulsion can be reduced to 219 mg/L after separation. More importantly, the performance remains good in the cycle test, and due to the construction of a durable superhydrophobic sponge, it can still maintain its relatively good performance in artificial seawater, acid-base environments, and can achieve relatively stable emulsion separation. At the same time, the potential of the polymer material composited with PDA in lasting and stable emulsion separation was also verified.

Reaction mechanism conversion induced by the contest of nucleophile and leaving group.

Direct dynamic simulations have been employed to investigate the OH- + CH3Cl reaction with the chosen B3LYP/aug-cc-pVDZ method. The calculated rate coefficient for the bimolecular nucleophilic substitution reaction (SN2), 1.0 × 10-9 cm3 mol-1 s-1 at 300 K, agrees well with the experimental result of (1.3-1.6) × 10-9 cm3 mol-1 s-1. The simulations reveal that the majority of the SN2 reactions are temporarily trapped in the hydrogen-bonded complex at Ecoll = 0.89 kcal mol-1. Importantly, the influences of the leaving group and nucleophile have been discussed by comparisons of X- + CH3Y (X = F, OH; Y = Cl, I) reactions. For the X = F- reactions, the reaction probability of SN2 increases along the increased leaving group ability Cl < I, suggesting that the thermodynamic factor plays a key role. The indirect mechanisms were found to be dominant for both reactions. In contrast, for X = OH-, the fraction of SN2 drops with the enhanced leaving group ability. In particular, a dramatic transition occurs for the dominant atomic reaction mechanisms, i.e., from complex-mediated indirect to direct, implying an interesting contest between the leaving group and the nucleophile and the importance of the dynamic factors, i.e., the dipole moment, steric hindrance, and electronegativity.

TMT-based proteomics analysis to screen potential biomarkers of Achyranthis Bidentatae Radix for osteoporosis in rats.

This study aimed to explore the possible mechanism of Achyranthis Bidentatae Radix for the treatment of osteoporosis using tandem mass tag-based proteomics technique combined with mass spectrometry. Proteomics techniques combined with bioinformatics were used to analyze the biological functions of differentially expressed proteins. In addition, western blotting was performed to verify the expression of related proteins. A total of 3,752 proteins were identifiable by proteomic analysis. Furthermore, 93 differentially expressed proteins were identified, of which 61 were upregulated and 32 were downregulated. Differentially expressed proteins were primarily associated with oxidative phosphorylation (p = 4.8 × 10-4 ) pathways and involved in transmembrane transport (p = 3.5 × 10-3 ), exocytic process (p = 1.2 × 10-2 ), cellular developmental process (p = 1.3 × 10-2 ), adenosine triphosphate metabolic process (p = 1.0 × 10-2 ) and other biological processes. Western blotting analysis showed that MT-CYB and NDUFA9 were differentially expressed in the bone microenvironment of rats with osteoporosis. We speculated that they were potential biomarkers linked to osteoporosis. This study employed proteomics to explore the potential therapeutic targets of Achyranthis Bidentatae Radix to treat osteoporosis. This revealed that mitochondria are a new target for the treatment of glucocorticoid-induced osteoporosis.

The effect of anti-alcoholic gastric ulcer before and after vinegar-processed Yuanhu Zhitong prescription based on spectral-effect relationship.

The aim of this study was to screen out the active ingredients of Yuanhu Zhitong prescription (YZP) before and after vinegar processing to play an anti-alcoholic gastric ulcer role through spectrum-effect relationship. First, the fingerprint of 16 batches of YZP was studied using the ultra-high-performance liquid chromatography-quadrupole mass spectrometry detector analysis (UPLC-QDA) method. Second, gastric lesion was induced by anhydrous ethanol. The degree of gastric mucosa injury was evaluated by hematoxylin and eosin staining, and the contents of malondialdehyde and tumor necrosis factor α and superoxide dismutase were detected using the enzyme-linked immunosorbent assay kit. Sixteen batches of YZP were analyzed using the spectrum-effect relationship method. Finally, absorption, distribution, metabolism, and excretion (ADME) was used to evaluate the bioavailability of potential compounds. The results showed that the UPLC-QDA method could successfully establish the fingerprint of YZP. Hematoxylin and eosin staining and biochemical indicators showed that YZP had obvious anti-alcoholic gastric ulcer action. Coptisine chloride, corydaline, berberine chloride, palmatine, imperatorin, and phellopterin were screened out using the spectrum-effect method, and all of them possessed good bioavailability. The results of this study suggest that YZP plays an anti-ulcer role by exerting antioxidant and anti-inflammatory effects through six main active components.

Synergistic Effects of B-F/B-S and Nitrogen Vacancy Co-Doping on g-C3N4 and Photocatalytic CO2 Reduction Mechanisms: A DFT Study.

Nonmetallic co-doping and surface hole construction are simple and efficient strategies for improving the photocatalytic activity and regulating the electronic structure of g-C3N4. Here, the g-C3N4 catalysts with B-F or B-S co-doping combined with nitrogen vacancies (Nv) are designed. Compared to the pristine g-C3N4, the direction of the excited electron orbit for the B-F-co-doped system is more matching (N2pz→C2pz), facilitating the separation of electrons and holes. Simultaneously, the introduced nitrogen vacancy can further reduce the bandgap by generating impurity states, thus improving the utilization rate of visible light. The doped S atoms can also narrow the bandgap of the B-S-Nv-co-doped g-C3N4, which originates from the p-orbital hybridization between C, N, and S atoms, and the impurity states are generated by the introduction of N vacancies. The doping of B-F-Nv and B-S-Nv exhibits a better CO2 reduction activity with a reduced barrier for the rate-determining step of around 0.2 eV compared to g-C3N4. By changing F to S, the origin of the rate-determining step varies from *CO2→*COOH to *HCHO→*OCH3, which eventually leads to different products of CH3OH and CH4, respectively.

Atomically Dispersed Pentacoordinated-Zirconium Catalyst with Axial Oxygen Ligand for Oxygen Reduction Reaction.

Single-atom catalysts (SACs), as promising alternatives to Pt-based catalysts, suffer from the limited choice of center metals and low single-atom loading. Here, we report a pentacoordinated Zr-based SAC with nontrivial axial O ligands (denoted O-Zr-N-C) for oxygen reduction reaction (ORR). The O ligand downshifts the d-band center of Zr and confers Zr sites with stable local structure and proper adsorption capability for intermediates. Consequently, the ORR performance of O-Zr-N-C prominently surpasses that of commercial Pt/C, achieving a half-wave potential of 0.91 V vs. reversible hydrogen electrode and outstanding durability (92 % current retention after 130-hour operation). Moreover, the Zr site shows good resistance towards aggregation, enabling the synthesis of Zr-based SAC with high loading (9.1 wt%). With the high-loading catalyst, the zinc-air battery (ZAB) delivers a record-high power density of 324 mW cm-2 among those of SAC-based ZABs.

Metal Chalcogenide Supertetrahedral Clusters: Synthetic Control over Assembly, Dispersibility, and Their Functional Applications.

ConspectusMetal chalcogenide supertetrahedral clusters (MCSCs) bear the closest structural resemblance to II-VI or I-III-VI semiconductor nanocrystals and can be considered as well-defined ultrasmall "quantum dots" (QDs). Compared to traditional colloidal QDs that are typically associated with size dispersity, irregular surface atomic structures, poorly defined core-ligand interfaces, and random defect/dopant sites, the nano- or subnano-sized MCSCs feature precise structural properties such as atomically uniform size, precise structure, and ordered dopant distribution, all of which offer ample opportunities for a broad and in-depth understanding of the correlation between the precise local structure and site- or size-dependent properties, which are critical to the exploitation of their functional applications. Our previous Account in 2005 provided a narrative on the efforts to expand the structural diversity of open-framework materials using different-sized and compositionally tunable clusters as building blocks with a primary objective of integrating the semiconducting properties with porosity in zeolite-type solids. Over the past 15 years, significant progress has been made, particularly in the synthetic control of discrete clusters, allowing the establishment of the composition-structure-property correlation of the MCSCs to guide the optimization of their properties for various applications. In the present Account, the recent progress in MCSC-based chemistry is reviewed from three aspects: (1) controllable synthesis of new members and types of MCSC models and the development of organic-ligand-directed hybrid assembly modes for MCSC-based open frameworks; (2) new synthetic strategies for the discretization of MCSCs in crystal lattice and their dispersibility in solvents, affording practical applications of pure inorganic MCSCs as nanomaterials; and (3) functionality of MCSC-based materials including photochemical and electrochemical properties triggered by precise dopant/defect sites, open-framework-related functional expansion via host-guest chemistry, and dispersed cluster-based composite materials with synergy from functional multimetallic components. All these advances show that MCSCs with well-defined structures and atomically precise dopant/defect sites are powerful model systems for establishing the precise structure-composition-property correlation and understanding the photophysical dynamic behaviors, both of which are difficult or impossible to achieve in the traditional QD system. Perspectives on their potential applications are presented in terms of the amorphous assemblies of monodispersed MCSCs, MCSC-based two-dimensional layered materials, and optical/electronic devices.

Direct dynamics in a proton transfer reaction of isomer product competition. Insight into the suppressed formation of the isoformyl cation.

Proton transfer between HOCO+ and CO produces the formyl cation HCO+ and isoformyl cation HOC+ isomers initiating multiple astrochemical reaction networks. Here, the direct chemical dynamics simulations are performed to uncover the underlying atomistic dynamics of the above reaction. The simulations reproduce the measured product energy and scattering angle distributions and reveal that the reaction proceeds predominantly through a direct stripping mechanism which results in the prominent forward scattering observed in experiments. The reaction dynamics show propensity for the HCO+ product even at a collision energy larger than the threshold for HOC+ formation. This is a consequence of the larger opacity and impact parameter range for HCO+. In accordance with the revealed direct mechanistic feature, the reaction can be controlled by orienting the reactants into a reactive H-C orientation that also favors HCO+ formation. Considering the lack of equilibrated reactant complexes and the on the fly migration of the proton, the CO2-catalyzed isomerization is assumed to have insignificant impact on the isomer ratios. This work provides insights of dynamical effects besides energetics into the interesting finding of strongly suppressed formation of the metastable isoformyl cation for related proton transfer reactions in the measurements.