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(PsycInfo Database Record (c) 2021 APA, all rights reserved).Mere observation of others experiencing stress is often sufficient to evoke stress vicariously, especially when people try to understand the situation from the viewpoint of others. Here, we tested whether and how the experience of vicarious stress, facilitated by perspective-taking, would influence individuals' affective and motivational reactions to an upcoming experience of firsthand stress-when they themselves encounter the same stressor in the future. Participants viewed a video clip of another participant undergoing a stressful task (a speech task), after being randomly assigned to take either a first-person perspective of the person (perspective-taking condition; n = 45) or maintain a detached, third-person, observer perspective (objective condition; n = 46). Subsequently, participants were given a surprise speech task and asked to prepare for their own speech for 2 minutes, during which their cardiovascular responses were assessed to differentiate motivational states of challenge or threat. Compared to participants in the objective condition, those in the perspective-taking condition perceived higher levels of stress in anticipation of giving a speech. The heightened stress appraisals, in turn, were associated with a more adaptive pattern of cardiovascular reactivity to the firsthand (relative to vicarious) stressor, characterized as challenge responses (an increase in cardiac output and a decrease in total peripheral resistance). These results suggest that perspective-taking enhances sensitivity to vicarious stress, which in turn, may facilitate preparedness for future stressors. Discussion centers on the functional adaptiveness of vicarious stress. (PsycInfo Database Record (c) 2021 APA, all rights reserved).In the current research, we apply a dyadic perspective of expressive suppression (ES) to test whether ES represents a weak link, such that either actors' or partners' ES is sufficient to undermine relationship satisfaction. Our primary aim was to test this weak-link pattern by modeling Actor × Partner ES interactions on relationship satisfaction. To maximize power, we conducted integrative data analyses across four existing dyadic samples (N = 427 couples) that included self-reports of habitual ES and relationship satisfaction. [https://www.selleckchem.com/products/tno155.html TNO155] Our second aim was to examine the role of conflict resolution ability as one potential mechanism for the ES weak-link pattern on satisfaction. These integrative data analyses involved two dyadic samples (N = 242 couples) that included self-reports of conflict resolution ability. Significant Actor × Partner ES interactions revealed a weak-link pattern greater actors' or partners' ES was associated with lower relationship satisfaction. Accordingly, actors' lower ES was associated with higher satisfaction only when partners' ES was also low. This ES weak-link pattern also emerged for conflict resolution ability, which provided evidence that reduced conflict resolution ability is one interpersonal process that contributes to the weak-link pattern on satisfaction. ES likely operates as a weak link because actors' or partners' ES interferes with the coordination, cooperation, and connection needed to manage relationship challenges and sustain healthy relationships. (PsycInfo Database Record (c) 2021 APA, all rights reserved).Recent research has demonstrated the adaptiveness of variability in emotion regulation (ER) by showing that variability between and, when controlled for depression, within ER strategies as assessed via the standard deviation was associated with less negative affect. We first replicated associations with negative affect by using the relative standard deviation, which is less confounded with the mean. Second, following research on affect dynamics, we extended this line of research by examining five additional ER dynamic measures covering ER instability, inertia, predictability, differentiation, and diversity. Reanalyzing data from five ambulatory assessment data sets (N = 717), we found that (a) the eight ER dynamic measures loaded on five factors that explained unique variance, (b) most ER dynamic measures had good reliabilities, and (c) between-strategy mean endorsement was positively, whereas between-strategy variability and ER predictability were negatively associated with negative affect. These results suggest that the variable but predictable use of emotion regulation strategies in daily life is beneficial for individuals' affective well-being in daily life. (PsycInfo Database Record (c) 2021 APA, all rights reserved).An unusual Namide···H-Namide hydrogen bond (HB) was previously proposed to stabilize the azapeptide β-turns. Herein we provide experimental evidence for the Namide···H-Namide HB and show that this HB endows a stabilization of 1-3 kcal·mol-1 and enforces the trans-cis-trans (t-c-t) and cis-cis-trans (c-c-t) amide bond conformations in azapeptides and N-methyl-azapeptides, respectively. Our results indicate that these Namide···H-Namide HBs can have stabilizing contributions even in short azapeptides that cannot fold to form β-turns.Psammocindoles A-C (1-3), a new class of indole alkaloids, were isolated from a Psammocinia vermis sponge. By combined spectroscopic analyses, the structures of these compounds were determined to be the indole-γ-lactams derived from three amino acid residues. In addition, an enantiomer psammocindole D (4), and the N-lactam isomers isopsammocindoles A-D (5-8) were also synthesized. These natural products and synthetic analogues were found to significantly stimulate adiponectin secretion in human bone marrow mesenchymal stem cells.An unprecedented cross-coupling reaction of alkyl carbagermatranes with bromofluoroolefins to deliver dialkyl-substituted monofluoroalkenes was achieved. This cross-coupling reaction was performed under base/additive-free conditions with excellent functional group tolerance, therefore offering an opportunity for challenging dialkyl-substituted monofluoroalkenes. The preparation of bioactive agent analogues including an antitubercular agent mimic and a COX-2 inhibitor analogue and the late-stage fluoroalkenylation of drug-molecule derivatives proved the utility of this strategy.The metal-free ring expansion of cyclopropanols containing a pendant styrene moiety was successfully achieved using a proton-coupled electron transfer enabled by an organic photoredox catalyst. Through this, variants of 1-tetralone and 1-benzosuberone bearing a substituent at the benzylic position were selectively obtained through the regioselective ring closure of alkyl radical intermediates depending on the substitution pattern of the alkene moiety.An efficient regioselective palladium(II)-catalyzed C(sp2)-H 4-acetoxylation of tryptophan and tryptophan-containing peptides is described. This transformation achieves the direct construction of C-O bonds at the tryptophan C4-position and features good functional group tolerance. The 4-hydroxyl compound was obtained by removing acetyl after C4-acetoxylation of tryptophan derivatives and tryptophan-containing dipeptides. This method provides a novel strategy for the synthesis of 4-substituted tryptophan derivatives and modification of tryptophan-containing peptides.An iron-sulfur complex formed by the simple mixture of FeCl3 with S3•- generated in situ from K2S is developed and applied to selective aerobic oxidation of terminal alkenes. The reaction was carried out under an atmosphere of O2 (balloon) and could proceed on a gram scale, expanding the application of S3•- in organic synthesis. This study also encourages us to explore the application of an Fe-S catalyst in organic reactions.A Ru(II)-catalyzed weak chelating group-aided ortho-C-H alkylation of arylamides with unactivated olefins in a redox-neutral fashion has been demonstrated. The present alkylation reaction was well-suited for various substituted arylamides and unactivated aliphatic alkenes. In this alkylation reaction, pivalic acid plays dual role in which it delivers the proton source in a protonation step and the corresponding acetate moiety deprotonates the ortho-C-H bond of the arylamides.The selective photodeprotection of the NVoc-modified FGG tripeptide yields the transformation of its 11 receptor-ligand complex with cucurbit[8]uril into a homoternary FGG2@CB8 assembly. The resulting light-induced dimerization of the model peptide provides a tool for the implementation of stimuli-responsive supramolecular chemistry in biologically relevant contexts.A visible-light-induced carbonylation of indoles with phenols for the synthesis of indole-3-carboxylates has been developed. The reaction proceeded via a radical carbonylation process in which elementary I2 was used as an effective photosensitive initiator and, thus, avoided the use of transition metal catalysts. A series of different aryl indole-3-carboxylates were prepared in moderate to good yields. The broad applicability of this methodology was further highlighted by the late-stage functionalization of several phenol-containing natural products and pharmaceuticals.Trajectories of atomic positions derived from ab initio molecular dynamics (AIMD) simulations of H-bonded liquids contain a wealth of information on dominant structural motifs and recurrent patterns of association. Extracting this information from a detailed search of the trajectories over multiple time frames is, however, a daunting exercise. Here, we use a machine learning strategy based on the neural inspired approach of the self-organizing maps (SOM), a type of artificial neural network that uses unsupervised competitive learning, to analyze the AIMD trajectories of liquid ethylene glycol (EG). The objective was to find whether there are H-bonded fragments, of two or more H-bonded EG molecules, that are recurrent in the liquid and to identify them. The SOM represents a set of high-dimensional data mapped onto a two-dimensional, grid of neurons or nodes, while preserving the topological properties of the input space. We show here that clustering of the fragments by SOM in terms of the molecular conformation of the individual EG molecules of the fragment and their H-bond connectivity pattern facilitates the search for H-bonded motifs. Using this approach, we are able to identify a H-bonded cyclic dimer and a bifurcated H-bonded structure as recurring motifs that appear in the longer H-bonded fragments present in liquid EG.A straightforward synthesis of a fluorine-18-labeled prodrug of AFA233 is reported. The key step in the preparation of [18F]AFA233-prodrug is the selective deprotection of the tert-butyl protection groups of the quinoxalinedione moiety without cleavage of the tert-butyl-S-acyl-2-thioethyl protection groups on the phosphate esters. In addition, the preparation of the nonradioactive prodrug reference compound of AFA233 is reported.RNAs are involved in an enormous range of cellular processes, including gene regulation, protein synthesis, and cell differentiation, and dysfunctional RNAs are associated with disorders such as cancers, neurodegenerative diseases, and viral infections. Thus, the identification of compounds with the ability to bind RNAs and modulate their functions is an exciting approach for developing next-generation therapies. Numerous RNA-binding agents have been reported over the past decade, but the design of synthetic molecules with selectivity for specific RNA sequences is still in its infancy. In this perspective, we highlight recent advances in targeting RNAs with synthetic molecules, and we discuss the potential value of this approach for the development of innovative therapeutic agents.