A High-Entropy Single-Atom Catalyst Toward Oxygen Reduction Reaction in Acidic and Alkaline Conditions.

The design of high-entropy single-atom catalysts (HESAC) with 5.2 times higher entropy compared to single-atom catalysts (SAC) is proposed, by using four different metals (FeCoNiRu-HESAC) for oxygen reduction reaction (ORR). Fe active sites with intermetallic distances of 6.1 Å exhibit a low ORR overpotential of 0.44 V, which originates from weakening the adsorption of OH intermediates. Based on density functional theory (DFT) findings, the FeCoNiRu-HESAC with a nitrogen-doped sample were synthesized. The atomic structures are confirmed with X-ray photoelectron spectroscopy (XPS), X-ray absorption (XAS), and scanning transmission electron microscopy (STEM). The predicted high catalytic activity is experimentally verified, finding that FeCoNiRu-HESAC has overpotentials of 0.41 and 0.37 V with Tafel slopes of 101 and 210 mVdec-1 at the current density of 1 mA cm-2 and the kinetic current densities of 8.2 and 5.3 mA cm-2, respectively, in acidic and alkaline electrolytes. These results are comparable with Pt/C. The FeCoNiRu-HESAC is used for Zinc-air battery applications with an open circuit potential of 1.39 V and power density of 0.16 W cm-2. Therefore, a strategy guided by DFT is provided for the rational design of HESAC which can be replaced with high-cost Pt catalysts toward ORR and beyond.

The relationship between clients' expectation of therapist support and challenge and treatment outcome: A response surface analysis.

Clients' expectations of treatment have long been posited as an important therapeutic factor in treatment success. Decades of research and meta-analytic findings have supported the notion that client expectations about what will happen over the course of therapy and how beneficial therapy will be are directly related to treatment factors, such as the working alliance and treatment outcome. Client expectations can be categorized into two broad categories, outcome expectations (i.e., how beneficial treatment will be) and treatment expectations (i.e., what will happen in treatment). This study sought to examine clients' treatment expectations, specifically, their role expectations, which represent their beliefs of how their therapists will act in session. Data for this study included 1,233 clients participating in individual counseling with 49 therapists at a university counseling center. Multilevel polynomial regression and response surface analysis were used to test congruent and discrepant effects of clients' pretreatment support and challenge expectancy on reductions in their psychological distress over the course of treatment. Results indicated that reductions in clients' psychological distress were the greatest when their support and challenge expectancy scores were congruent and high. In other words, clients who expected both high challenge and high support from their therapist, prior to the start of counseling, reported the greatest improvement in counseling. Clients similarly reported reductions in their psychological distress when their support and challenge expectations were congruent and low, although this effect was smaller than when they expected high levels of both support and challenge. Together, these findings suggest that when clients' expectations of support and challenge are similar, they fare better in treatment, as opposed to when they expect a greater amount of support than challenge or vice versa. (PsycInfo Database Record (c) 2022 APA, all rights reserved).

Machine Learning-Aided Design of Gold Core-Shell Nanocatalysts toward Enhanced and Selective Photooxygenation.

We demonstrate the use of the machine learning (ML) tools to rapidly and accurately predict the electric field as a guide for designing core-shell Au-silica nanoparticles to enhance 1O2 sensitization and selectivity of organic synthesis. Based on the feature importance analysis, obtained from a deep neural network algorithm, we found a general and linear dependent descriptor (θ ∝ aD0.25t-1, where a, D, and t are the shape constant, size of metal nanoparticles, and distance from the metal surface) for the electric field around the core-shell plasmonic nanoparticle. Directed by the new descriptor, we synthesized gold-silica nanoparticles and validated their plasmonic intensity using scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS) mapping. The nanoparticles with θ = 0.40 demonstrate an ∼3-fold increase in the reaction rate of photooxygenation of anthracene and 4% increase in the selectivity of photooxygenation of dihydroartemisinic acid (DHAA), a long-standing goal in organic synthesis. In addition, the combination of ML and experimental investigations shows the synergetic effect of plasmonic enhancement and fluorescence quenching, leading to enhancement for 1O2 generation. Our results from time-dependent density functional theory (TD-DFT) calculations suggest that the presence of an electric field can favor intersystem crossing (ISC) of methylene blue to enhance 1O2 generation. The strategy reported here provides a data-driven catalyst preparation method that can significantly reduce experimental cost while paving the way for designing photocatalysts for organic drug synthesis.

Elimination of Uremic Toxins by Functionalized Graphene-Based Composite Beads for Direct Hemoperfusion.

Conventional absorbents for hemoperfusions suffer from low efficiency and slow absorption with numerous side effects. In this research, we developed cellulose acetate (CA) functionalized graphene oxide (GO) beads (∼1.5-2 mm) that can be used for direct hemoperfusion, aiming at the treatment of kidney dysfunction. The CA-functionalized GO bead facilitates adsorption of toxins with high biocompatibility and high-efficiency of hemoperfusion while maintaining high retention for red blood cell, white blood cells, and platelets. Our in vitro results show that the toxin concentration for creatinine reduced from 0.21 to 0.12 µM (p < 0.005), uric acid from 0.31 to 0.15 mM (p < 0.005), and bilirubin from 0.36 to 0.09 mM (p < 0.005), restoring to normal levels within 2 h. Our in vivo study on rats (Sprague-Dawley, n = 30) showed that the concentration for creatinine reduced from 83.23 to 54.87 µmol L-1 (p < 0.0001) and uric acid from 93.4 to 54.14 µmol L-1 (p < 0.0001), restoring to normal levels within 30 min. Results from molecular dynamics (MD) simulations using free-energy calculations reveal that the presence of CA on GO increases the surface area for adsorption and enhances penetration of toxins in the binding cavities because of the increased electrostatic and van der Waals force (vdW) interactions. These results provide critical insight to fabricate graphene-based beads for hemoperfusion and to have the potential for the treatment of blood-related disease.

Perceptions of masculinity and fatherhood among men experiencing homelessness.

This study explored the perceptions of fatherhood held by 11 men living in a homeless shelter. Using consensual qualitative research methodology (CQR; Hill, 2012), we investigated perceptions of masculinity and fatherhood among fathers experiencing homelessness. Participants described (a) their perceptions of masculinity and fatherhood and changes resulting from homelessness, (b) physical and psychological challenges of being a father experiencing homelessness, and (c) expectations of homeless fathers. The fathers generally expressed feelings of low self-esteem related to their perceived difficulty fulfilling the role of providers for their family; however, they also adapted their view of fatherhood to include roles suited to their situation, such as that of guide, teacher, and role model. Suggestions are made for clinicians in helping fathers navigate and develop these roles, and limitations and directions for future research are discussed. (PsycINFO Database Record