Mechanisms of a mindfulness psyCho-behAvioRal intErvention (MCARE) on depression and anxiety symptoms in patients with acute coronary syndrome: A longitudinal mediation analysis.

OBJECTIVE: This study aimed to explore the mediating roles of mindfulness and illness perception in the effects of a social media-based Mindfulness psyCho-behAvioRal intErvention (MCARE) on depressive and anxiety symptoms among patients with ACS. METHODS: This study conducted a secondary longitudinal mediation analysis using data from a randomized controlled trial of the MCARE grogram in patients with ACS. Participants were recruited at two tertiary hospitals in Jinan, China. The MCARE program consisted of six weekly sessions addressing mindfulness training and disease management to facilitate understanding and management of emotions and illness. The analytical sample included participants who completed measures of the primary outcomes, i.e., depression (PHQ-9) and anxiety (GAD-7) and potential mediators, i.e., mindfulness (CAMS-R) and illness perception (Brief-IPQ) at baseline (T0), immediate post-intervention (T1), and 12-week after the commencement of the intervention (T2). RESULTS: This study included 146 participants (mean age 58.9 years (SD = 8.9), 69.2 % male), including both intervention and control groups. The mediation analysis revealed a significant mediating effect of T1 mindfulness in the relationship between the group and T2 depression symptoms (indirect effect: -0.109, 95 % CI: -0.191, -0.041; P = 0.004), accounting for 26 % of the effect. For T2 anxiety symptoms, T1 illness perception exhibited a significant mediating effect (indirect effect: -0.055, 95 % CI: -0.110, -0.005; P = 0.035), accounting for 22 % of the effect. CONCLUSIONS: This study found that mindfulness and illness perception played a mediating role in the effects of the MCARE program on depressive and anxiety symptoms among patients with ACS.

Relationships between disease severity, psychological stress, and health-related quality of life among patients with acute coronary syndrome: mediation of illness perception.

AIMS: Patients with acute coronary syndrome (ACS) often experience reduced health-related quality of life (HRQOL), which may be attributable to the disease severity and psychological stress. While illness perception is speculated to be a potential pathway underlying these relationships, evidence supporting this mechanism remains limited. This study aimed to investigate the relationships between disease severity, psychological stress, and HRQOL and whether these relationships are mediated by illness perception in patients with ACS. METHODS AND RESULTS: Data were collected from June to July 2019 and June to September 2020 in the cardiology departments of four public hospitals in China. Eligible patients completed measures of disease severity, psychological stress, illness perception, HRQOL, and socio-demographic and clinical characteristics. Data were analysed employing hierarchical multiple regression and structural equation modelling. This study included 405 participants (mean age 60.63 years, 67.4% male). After controlling for socio-demographic and clinical covariates, higher levels of disease severity (ß = 0.115, P = 0.024) and psychological stress (ß = -0.209, P＜0.001) were associated with poorer HRQOL; however, the relationships became non-significant after adding illness perception into the regression model. Structural equation modelling analysis suggested that illness perception played a mediating role between disease severity, psychological stress, and HRQOL, accounting for 45.95% and 65.79% of the total effects, respectively. CONCLUSION: This study found that illness perception mediated the relationships between disease severity, psychological stress, and HRQOL among patients with ACS. Improving patients' HRQOL should consider its important influencing factors with a focus on promoting positive illness perception.

Efficient Liberation of Ammonia from Thermal Reaction of ScNH+ Cations and Water.

Ammonia synthesis by using water as a hydrogen source is a challenging task. Laser-ablation-generated ScNH+ cations have been mass-selected using a quadrupole mass filter and reacted with H2O in a linear ion trap reactor under thermal collision conditions. Through mass spectrometry in conjunction with density functional theory calculations, we found that ammonia is released as the product in the reaction of ScNH+ with H2O, and this reaction is with high efficiency and selectivity, and the rate constant for the reaction is (1.14 ± 0.23) × 10-10 cm3 molecule-1 s-1, corresponding to the reaction efficiency of 15%. Metal imido complexes (*MNH) are one of the important intermediates in the currently reported NH3 synthetic reactions. The gas-phase ScNH+ cation can be a simplified model of *MNH over catalysts of NH3 synthesis, and the facile proton transfer mechanism obtained in this model system may offer fundamental mechanistic insights into how to design catalysts for ammonia production by using water as the hydrogen source under ambient conditions.

Dinitrogen Fixation and Reduction by Ta3N3H0,1- Cluster Anions at Room Temperature: Hydrogen-Assisted Enhancement of Reactivity.

Dinitrogen activation and reduction is one of the most challenging and important subjects in chemistry. Herein, we report the N2 binding and reduction at the well-defined Ta3N3H- and Ta3N3- gas-phase clusters by using mass spectrometry (MS), anion photoelectron spectroscopy (PES), and quantum-chemical calculations. The PES and calculation results show clear evidence that N2 can be adsorbed and completely activated by Ta3N3H- and Ta3N3- clusters, yielding to the products Ta3N5H- and Ta3N5-, but the reactivity of Ta3N3H- is five times higher than that of the dehydrogenated Ta3N3- clusters. The detailed mechanistic investigations further indicate that a dissociative mechanism dominates the N2 activation reactions mediated by Ta3N3H- and Ta3N3-; two and three Ta atoms are active sites and also electron donors for the N2 reduction, respectively. Although the hydrogen atom in Ta3N3H- is not directly involved in the reaction, its very presence modifies the charge distribution and the geometry of Ta3N3H-, which is crucial to increase the reactivity. The mechanisms revealed in this gas-phase study stress the fundamental rules for N2 activation and the important role of transition metals as active sites as well as the new significant role of metal hydride bonds in the process of N2 reduction, which provides molecular-level insights into the rational design of tantalum nitride-based catalysts for N2 fixation and activation or NH3 synthesis.

Clean and Efficient Transformation of CO2 to Isocyanic Acid: The Important Role of Triatomic Cation ScNH.

Achieving the desired selective transformations of the very stable CO2 into useful chemicals is quite important for the development of economically and environmentally sustainable synthetic methods. Herein, mass spectrometric experiments and quantum-chemical calculations have identified that ScNH+ reacts quite efficiently with CO2 under thermal collision conditions to exclusively yield ScO+ and isocyanic acid (HNCO). This is a novel reaction type in CO2 activation reactions mediated by gas-phase ions. In this reaction, the C═N double bond has also been formed for the first time in the gas phase. The mechanism of "migratory insertion" is proposed. Coupled with the previously reported reaction of Sc+ with NH3, HNCO can be synthesized under mild conditions from NH3 and CO2 in quite simple reactions. The mechanistic information gained in this gas-phase model reaction can offer fundamental insights relevant to corresponding processes and further guide on how to design brand new catalysts.

Hydrogen- and oxygen-atom transfers in the thermal activation of benzene mediated by Cu2O2+ cations.

The mass-selected copper oxide cluster cations Cu2O2+ are successfully prepared by laser ablation and reacted with benzene in a linear ion trap reactor. The cluster reaction is characterized by reflectron mass spectrometry in conjunction with density functional theory calculations. Four types of reaction channels are observed: (1) Cu2OH+ + C6H5O˙, (2) Cu2C6H6+ + O2, (3) Cu(C6H6)2+ + Cu and (4) Cu2O2C6H6+, in which the first one is the major product. Observation of the products Cu2OH+ indicates that oxygen atom transfer (OAT) accompanying hydrogen atom transfer (HAT) occurs, and the oxygen-centered radical (O-˙) in Cu2O2+ is crucial to the cleavages of C-H and Cu-O bonds. It is interesting that HAT and OAT occur in a single reaction channel to form C6H5O˙, which has not been reported in the reactions of gas-phase ions with benzene. The calculated results are in agreement with the experimental observations, and no two-state reactivity scenario is present in the potential energy surface of channel 1. This work can provide useful insights into the nature of active sites over copper oxides and reaction mechanisms in the corresponding heterogeneous reactions.

Direct hydroxylation of benzene to phenol mediated by nanosized vanadium oxide cluster ions at room temperature.

Gas-phase vanadium oxide cluster cations and anions are prepared by laser ablation. The small cluster ions (<1000 amu) are mass-selected using a quadrupole mass filter and reacted with benzene in a linear ion trap reactor; large clusters (>1000 amu) with no mass selection are reacted with C6H6 in a fast flow reactor. Rich product variety is encountered in these reactions, and the reaction channels for small cationic and anionic systems are different. For large clusters, the reactivity patterns of (V2O5) n+ (n = 6-25) and (V2O5) n O- (n = 6-24) cluster series are very similar to each other, indicating that the charge state has little influence on the oxidation of benzene. In sharp contrast to the dramatic changes of reactivity of small clusters, a weakly size dependent reaction behavior of large (V2O5)6-25+ and (V2O5)6-24O- clusters is observed. Therefore, the charge state and the size are not the major factors influencing the reactivity of nanosized vanadium oxide cluster ions toward C6H6, which is not common in cluster science. In the reactions with benzene, the small and large reactive vanadium oxide cations show similar reactivity of hydroxyl radicals (OH•) toward C6H6 at higher and lower temperatures, respectively; different numbers of vibrational degrees of freedom and the released energy during the formation of adduct complexes can explain this intriguing correlation. The reactions investigated herein might be used as the models of how to realize the partial oxidation of benzene to phenol in a single step, and the observed mechanisms are helpful to understand the corresponding heterogeneous reactions, such as those over vanadium oxide aerosols and vanadium oxide catalysts.

Fe2 O+ Cation Mediated Propane Oxidation by Dioxygen in the Gas Phase.

The mass-selected Fe2 O+ cation mediated propane oxidation by O2 was investigated by mass spectrometry and density functional theory calculations. In the reaction of Fe2 O+ with C3 H8 , H2 was liberated by C-H bond activation to give Fe2 OC3 H6+ . Interestingly, when a mixture of C3 H8 /O2 was introduced into the reactor, an intense signal that corresponded to the Fe2 O2+ cation was present; the experiments indicated that O2 was activated in its reaction with Fe2 O(C3 H6 )+ to give Fe2 O2+ and C3 H6 O (acetone or propanal). A Langmuir-Hinshelwood-like mechanism was adopted in the propane oxidation reaction by O2 on gas-phase Fe2 O+ cations. In comparison with the absence of Fe2 O2+ in the reaction of Fe2 O+ with O2 , the ligand effect of C3 H6 on Fe2 OC3 H6+ is important in the oxygen activation reaction. The theoretical results are consistent with the experimental observations. The propane oxidation by O2 in the presence of Fe2 O+ might be applied as a model for alkane and O2 activations over iron oxide catalysts, and the mechanisms and kinetic data are useful for understanding corresponding heterogeneous reactions.