Insights into the Luminescence Quantum Yields of Cyclometalated Iridium(III) Complexes: A Density Functional Theory and Machine Learning Approach.

Cyclometalated iridium(III) complexes have been used in various optical materials, including organic light-emitting diodes (OLEDs) and photocatalysts, and a deeper understanding and prediction of their luminescence quantum yields (LQYs) greatly aid in accelerating material design. In this study, we integrated density functional theory (DFT) calculations with machine learning (ML) techniques to extract factors controlling LQY. Although a substantial data set of Ir(III) complexes and their LQYs is indispensable for constructing accurate ML models to predict LQYs, generating this type of data set is challenging due to the complexities associated with ab initio calculations of LQYs. To address this issue, we investigated the nonradiative decay process of nine Ir(III) complexes emitting blue to green, each exhibiting varying experimental LQYs, by using DFT calculations. For all nine complexes, the quenching process was induced by the rotation of the single bond in one of the ligands, which converted the six-coordinate structure to the five-coordinate structure. Since the decay mechanism was common for the nine Ir(III) complexes, parameters correlated with LQYs could be used as objective variables instead of LQYs. Based on this idea, we collected a data set featuring Ir(III) complexes and the energy differences between their six- and five-coordinate triplet structures, which correlated with LQYs. We also constructed ML models using the calculated LQYs as the objective variables with the parameters from the ground-state calculations as explanatory variables. The analyses of the constructed model revealed that the LUMO energy of the ligand made the most significant negative contribution to LQY. This suggests that the potential energy surface of the metal-to-ligand charge transfer (MLCT) excited state, which stabilizes the six-coordinate structure, is reduced by decreasing the energy of the unoccupied orbitals.

Can probability neglect bias promote social distancing during the COVID-19 pandemic?

The effectiveness of a stay-at-home order depends on the speed of behavioral changes that are triggered by risk perception. Probability neglect bias, one of the cognitive biases, may lead people to engage in social distancing. However, there is no empirical evidence of the relationship between probability neglect bias and social distancing. This study aims to examine the relationship between individual differences in susceptibility to probability neglect bias and the level of social distancing practice during the early stages of the COVID-19 outbreak in Japan. The level of engagement in social distancing was defined as the narrowing of life-space mobility. We conducted a web-based questionnaire survey among 1000 adults living in central Tokyo, Japan, at the beginning of the pandemic outbreak. Our results show that people had a strong fear of infection in the early pandemic stages. Approximately 60% of our subjects were influenced by probability neglect bias. People susceptible to probability neglect bias engaged in social distancing more intensely than those who were not susceptible after the state of emergency was lifted.

Characterization of the one-electron oxidized Cu(II)-salen complexes with a side chain aromatic ring: the effect of the indole ring on the Cu(II)-phenoxyl radical species.

To gain insights into the role of the proximal indole ring in the redox-active metal center as seen in galactose oxidase, we prepared the Cu(II)-salen-type complexes having a pendent indol-3-ylmethyl (1), methyl (2) or benzyl (3) group substituted on the ethylenediamine moiety and investigated the structures and redox properties by various physicochemical methods and theoretical calculations. Neutral complexes 1, 2, and 3 showed no significant difference in the UV-Vis-NIR and EPR spectra. One-electron oxidation of 1, 2, and 3 by addition of 1 equiv. of thianthrenyl radical gave [1]SbCl 6 , [2]SbCl 6 , and [3]SbCl 6 , respectively, which could be assigned to relatively localized phenoxyl radical species. The cyclic and differential pulse voltammograms of [1]SbCl 6 showed two redox waves with a large separation between the first and second redox potentials compared with the separations observed for [2]SbCl 6 and [3]SbCl 6 . This suggests that [1]SbCl 6 is more stabilized than [2]SbCl 6 and [3]SbCl 6 . The NIR band of [1]SbCl 6 showed a larger blue shift than that of [2]SbCl 6 and [3]SbCl 6 . The EPR spectrum of [2]SbCl 6 exhibited an intense signal at the g value of 2 due to partial disproportionation to form the EPR active two-electron oxidized complex [2] 2+ , while the EPR intensity of [1]SbCl 6 was much weaker than that of [2]SbCl 6 . These results indicate that the pendent indole moiety stabilizes the Cu(II)-phenoxyl radical in [1]SbCl 6 most probably by stacking with the phenoxyl moiety, which is further supported by DFT calculations.

Psychological Reactance to Mobility Restrictions Due to the COVID-19 Pandemic: A Japanese Population Study.

In Japan, mobility restrictions were enforced by the government to abate the spread of COVID-19. The current study examined whether experiences of such mobility restrictions affected motivation for future going-out activities. To this end, we conducted a one-time online survey of 1,000 adults in Tokyo to measure going-out activities in four different time periods at once: before the spread of infection, during and after the emergency declaration, and after the end of the pandemic (future desire). In addition, to examine the impact of preferences for online services that make it easier to stay home, we measured the usage history of online services to obtain food during the mobility restriction period. Results indicated that desire for going-out activities after the end of the pandemic increased compared with those before the pandemic, particularly for leisure-related purposes. In addition, the use of online services to obtain food tended to suppress the increased desire for future going-out activities, although this effect was not significant. In conclusion, mobility restrictions resulted in motivational arousal for going-out activities after the end of the pandemic. Our findings indicate that psychological reactance plays a role in determining going-out activities in the future.

Exploring the full catalytic cycle of rhodium(i)-BINAP-catalysed isomerisation of allylic amines: a graph theory approach for path optimisation.

We explored the reaction mechanism of the cationic rhodium(i)-BINAP complex catalysed isomerisation of allylic amines using the artificial force induced reaction method with the global reaction route mapping strategy, which enabled us to search for various reaction paths without assumption of transition states. The entire reaction network was reproduced in the form of a graph, and reasonable paths were selected from the complicated network using Prim's algorithm. As a result, a new dissociative reaction mechanism was proposed. Our comprehensive reaction path search provided rationales for the E/Z and S/R selectivities of the stereoselective reaction.

Is the useful field of view a good predictor of at-fault crash risk in elderly Japanese drivers?

AIM: Although age-related decline in the useful field of view (UFOV) is well recognized as a risk factor for at-fault crash involvement in elderly drivers, there is still room to study its applicability to elderly Japanese drivers. In the current study, we thus examined the relationship between UFOV and at-fault crash history in an elderly Japanese population. We also explored whether potential factors that create awareness of reduced driving fitness could be a trigger for the self-regulation of driving in elderly drivers. METHODS: We measured UFOV and at-fault crash history from 151 community-dwelling Japanese aged 60 years or older, and compared UFOV of at-fault crash-free and crash-involved drivers. We also measured self-evaluated driving style using a questionnaire. RESULTS: UFOV in crash-involved drivers was significantly lower than that in crash-free drivers. No significant difference was found in self-evaluated driving style between crash-free and crash-involved drivers. In addition, there was no significant association between UFOV and self-evaluated driving style. CONCLUSIONS: The present study showed that UFOV is a good predictor of at-fault crash risk in elderly Japanese drivers. Furthermore, our data imply that it might be difficult for elderly drivers to adopt appropriate driving strategies commensurate with their current driving competence.

Impact of HMG-CoA reductase inhibitors for non-treated coronary segments.

BACKGROUND: HMG-CoA reductase inhibitors (statin) have been reported to decrease coronary artery events in several angiographic studies. However, the mechanism by which statin achieve this is still unclear. The purpose of this study was to identify the effect of statin on coronary plaque using serial intravascular ultrasound analysis. METHODS AND RESULTS: In this study, 48 patients with 48 lesions were divided into the prescribed group (statin group, n = 22) or the non-prescribed group (control group, n = 26) after successful coronary artery stenting. IVUS images were obtained at consecutive 5 mm segments, 5 mm from the proximal stent edge, immediately after stenting and at 6 months follow up. External elastic membrane volume (EEMV), lumen volume (LV) and plaque volume (PV) were measured using Simpson's method. The control group revealed no significant serial change in EEMV, PV, and LV during 6 months. On the other hand, the statin group revealed significant reductions of PV (35.5 +/- 12.7 mm3 vs 30.9 +/- 15.6 mm3, p = 0.001), resulting in increase of LV (47.7 +/- 19.8 mm3 vs 52.5 +/- 22.2 mm3, p = 0.003) without EEMV change (82.8 +/- 21.8 mm3 vs 83.9 +/- 25.7 mm3, p = NS). Although percent EEMV and percent LV changes showed no differences between the two groups, a larger percent PV change was observed in the statin group compared to the control group (control; 5.8 +/- 20.3% vs statin; -20.4 +/- 21.8%, p = 0.02). CONCLUSION: The results of this study suggest that statin administration for 6 months reduces coronary plaque without positive vessel remodeling.

The gravitation of the moon plays pivotal roles in the occurrence of the acute myocardial infarction.

Acute myocardial infarction (AMI) is a social burden. However, being able to predict AMI could lead to prevention. A previous study showed only the relation between the lunar phase and the occurrence of AMI, but the period it takes for the moon to orbit around the earth and the period of the lunar phase differ. This study investigated the effect of the gravitation of the moon on AMI. Data was comprised of 1369 consecutive patients with first AMI at 5 hospitals from October, 1984 to December, 1997. The universal gravitation of the moon was calculated and compared to the earth onset time of AMI. Universal gravitation of the moon was derived by G*m/d(2) (G: universal gravitation constant, m: the mass of the moon, d: the distance between the center of the moon and the center of the earth). The relationship between m/d(2) and the cases of AMI was determined. There was an increase in cases, when there is a distance of more than 399864 km from the center of the earth to the center of the moon. The gravitation of more than 399864 km was determined to be weaker gravitation. It is confirmed that the number of AMI patients significantly increases at weaker gravitation periods in this multicenter trial. In conclusion, these results suggest that the gravitation of the moon may have an influence on the occurrence of AMI.