Helmssheehan1537

This study examines developmental change across adolescence in the similarity of friends versus nonfriends. This differential in similarity is a key aspect of the organization of the peer context of development The stronger the correlation between friends for an attribute, the more the attribute delineates clustering and divisions of friendships. We investigated change in the correlation between friends across 12 attributes covering demographics, orientations to key institutions (family, school, religion), and problem behavior, and we expected that the link between similarity and friendship would increase during adolescence for most attributes other than gender. We also predicted that the social ecological factors of school size and attribute variability would be associated with stronger correlations between friends and partially mediate developmental change. Data are from two grade cohorts of 27 small school districts, followed from sixth through 11th grades (N = 454 time-specific networks and over 65,000 person/waves of data; 84.2% White, 6.8% Hispanic/Latino, 3.2% African American, 1.3% Asian, .5% Native American, 3.9% other or multiple). The data analysis takes the form of a three-level random effects meta-analysis of network level correlations between friends (Moran's I). As expected, declining dominance of gender was offset by the emergence of moderate correlations across a broader profile of attributes. The ecological opportunity factors of grade cohort size and attribute variability significantly mediated these increases in correlations between friends, accounting for 23 to 73% of age-related change for 10 of the 11 attributes other than gender. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Caregivers are often encouraged to praise children to reduce externalizing behavior. Although several theoretical perspectives suggest that praise works (e.g., praise reinforces positive behavior), others suggest it may not (e.g., children dismiss praise or experience it as controlling). This longitudinal-observational study examined whether (a) caregivers' praise and children's externalizing behavior were related; (b) an evidence-based parenting program increased caregivers' praise; (c) and increasing praise reduced children's externalizing behavior. Participants (387 caregiver-child dyads) were randomly assigned to a 14-session parenting program (aiming to improve parenting behavior, partly via praise) or a control group. Children (aged 4-8 years, 45% girls) scored at or above the 75th percentile on externalizing behavior problems. Caregivers (91% Caucasian, 85% born in the Netherlands, 50.5% highly educated) were mostly mothers (91%). At baseline, postintervention, and follow-up, we assessed caregivers' labeled and unlabeled praise via in-home observations, and children's externalizing behavior via caregiver-reports and observations. At baseline, caregivers' unlabeled praise was related to more (rather than less) externalizing behavior. The parenting program successfully increased praise and reduced caregiver-reported (but not observed) externalizing behavior; importantly, however, praise did not mediate the program's effect on caregiver-reported externalizing behavior. Although the program did not directly reduce observed externalizing behavior, it did so indirectly via labeled praise. Our results suggest that, although praise and externalizing child behavior are related, praise may not be a key mechanism underlying the effects of the parenting program. If praise has beneficial effects on children's externalizing behavior, these effects are probably limited to labeled praise. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Past meta-analyses show that both child-mother and child-father attachment insecurity are independently and jointly associated with more externalizing behaviors in children. Little is known, however, on the ways that different types of insecure attachment independently and jointly predict the development of externalizing behaviors over time. Existing work also neglects the impact of children's gender within the context of child-father relationships. The current study addresses these limitations by investigating how insecure type of child-father attachment, child-mother attachment, and their interaction in the preschool years predict boys' and girls' externalizing behaviors in middle childhood, when controlling for children's externalizing behaviors in the preschool years. The sample included 144 preschool-aged children (M = 46.89 months, SD = 8.77, 83 girls) and both of their parents. At Time 1, children completed independent separation-reunion procedures with each parent, which were coded using the Preschool Attachment Rating Scales. At Time 1 and Time 2 (5 years later), mothers and fathers completed the Strengths and Difficulties Questionnaire to report on their children's externalizing behaviors. Results showed no systematic differences in the way that child-mother and child-father attachment predicted the development of externalizing behaviors in boys and girls. Across all children, results identified an interaction of child-father and child-mother ambivalence, by which the presence of ambivalence toward both parents predicted the development of more externalizing behaviors. In addition, child-father controlling-caregiving attachment predicted the development of fewer externalizing behaviors. These results provide insight into the ways that insecure child-father and child-mother attachment predict later socioemotional adaptation. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Extensive evidence and theory suggest that the development of motor skills during infancy and early childhood initiates a "developmental cascade" for cognitive abilities, such as reading and math. Motor skills are closely connected with the development of spatial cognition, an ability that supports deductive reasoning. Despite the linkage between motor skills and spatial cognition, and spatial cognition with deductive reasoning, no research has explored the developmental connection between early motor skills and reasoning ability, a plausible pathway through which the developmental cascade operates. Drawing data from the 1970 British Cohort Study (N = 1,233; 95% British, 5% other race/ethnicity; 54% male, 46% female; 7% low income, 80% middle income, 12% high income), this study investigated whether there was a relationship between gross and fine motor skills in infancy (22 months of age) and early childhood (42 months of age) and visuospatial deductive reasoning in adolescence (at 10 and 16 years of age). Results indicated that fine but not gross motor skills during early childhood positively predicted reasoning in adolescence. Critically, the fine motor-reasoning association mediated the previously observed link between early fine motor skills and adolescent reading and math ability. These results deepen our understanding of developmental cascade theory and mental model theory by identifying visuospatial reasoning (i.e., mental modeling) as a potential mechanism through which motor skills initiate cognitive development and academic success in reading and math. These findings also highlight the importance of early intervention programs targeting motor skills and illuminate the impact of those interventions on later cognitive and academic skills. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Serotonin is an important modulator of feeding behavior across animal species. In invertebrates, much is known about the regulation of feeding in several model organisms, but comparative data are limited. We examined the modulation of feeding behavior in crayfish by administering serotonin and two serotonin receptor ligands, mianserin and 5-carboxamidotryptamine. We found that, compared to control injections, exogenous serotonin significantly reduced appetitive behaviors in response to a chemical food stimulant and reduced consumption when food was present. The two ligands also significantly reduced the amount of food consumed. However, they had no significant effects on appetitive feeding movements, suggesting that appetitive and consummatory feeding phases may be regulated by different serotonergic mechanisms. (PsycInfo Database Record (c) 2022 APA, all rights reserved).We studied the role of dopamine [tyrosine hydroxylase (TH)] neurons in the rat ventral tegmental area (VTA) in safety learning. First, we used an AX +/BX-discrimination procedure to establish conditioned stimulus (CS) B as a learned safety signal that passed both summation and retardation tests of conditioned inhibition. Then, we combined this procedure with fiber photometry in TH-Cre rats to study the activity of VTA dopamine neurons during safety learning. We show that whereas footshock is associated with calcium transients in TH neurons across the VTA, shock omission during safety learning is selectively associated with calcium transients in dopamine neurons in the medial but not lateral VTA. Moreover, the magnitude of medial VTA calcium transients during shock omission accurately predicts the amount of safety that is learned and expressed during summation testing. Our findings are consistent with a common medial VTA dopamine mechanism contributing to the learned inhibition of fear in extinction and safety. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Memorializes Ravenna M. Helson (1925-2020). Helson was a pioneering feminist researcher whose studies advanced the understanding of women's development and creativity, and revealed the power of personality across the life span. She spent her 55-year career at the University of California Berkeley's Institute for Personality Assessment and Research. In 1955, she was the only woman on staff, and remained the only woman for decades. In 1958 with a 2- and a 1-year-old in tow, she launched the Mills Longitudinal Study of creative potential in 142 female seniors at Mills College. In those times, before second wave feminism or a women's movement, and without any psychology of women, she worked hard to attain visibility for her findings. In 1980 the Mills study transformed to a 50-year research program about women's adult development. Helson died October 2, 2020. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Memorializes Jerome L. Singer (1924-2019). Singer's seminal research, conducted over 50þ years, laid the foundations for virtually all modern investigations of stream of consciousness and mind wandering. During a time when daydreaming was considered pathological, Singer showed it to be a pervasive aspect of human experience that served positive social and creative functions, earning him the moniker "the father of daydreaming." After receiving his PhD in clinical psychology in 1951, Singer was certified as a psychoanalyst through the William Alanson White Institute, while also holding several part-time research appointments. In 1963, Singer became director of the clinical psychology program at City University, where he and collaborator John Antrobus studied "decoupled attention." Singer joined the faculty of Yale University in 1972 and assumed emeritus status in 2006. At Yale, he worked closely with his wife Dorothy (who was an exemplary developmental psychologist in her own right), where they codirected Yale's Family TV Research and Consultation Center for more than 30 years. He died on December 14, 2019. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Pfund and Hill (2022) suggest that individual resilience factors such as agreeableness and conscientiousness are likely to promote better relationship functioning as couples navigate the pandemic. Although we agree that more fully incorporating individual resilience factors would strengthen our adapted vulnerability-stress-adaptation (VSA) model, neither agreeableness nor conscientiousness reliably predict relationship functioning. In line with the VSA model, we emphasize the importance of a Person × Context approach that examines the potential effects of personality factors within couples' specific situational contexts during and after the pandemic. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Pietromonaco and Overall (2020) made an important contribution to the relationship literature when adapting Karney and Bradbury (1995) vulnerability-stress-adaptation model to include the COVID-19 pandemic. While the authors discussed ways in which enduring individual vulnerabilities may play a role in harming romantic relationships during the pandemic, only considering individual differences that may have negative implications for relationship functioning could lead to a limited perspective. The current comment discusses how conscientiousness and agreeableness may promote better relationship functioning during the COVID-19 pandemic. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Eating disorders (EDs) are serious psychiatric disorders that affect 13%-18% of young men and women. EDs are associated with substantial psychiatric and medical morbidity and mortality, indicating a critical need for improved identification and treatment. Despite the relatively high prevalence and severity of EDs, they are often omitted from discussions of mental health. This comment is in response to Gruber et al. (2020), who wrote an important article on the challenges and opportunities facing clinical scientists in the time of COVID-19. Our response extends Gruber et al.'s article by noting additional challenges facing people with an ED during COVID-19 and recognizing opportunities for improved evidence-based assessment and treatment of this important population. (PsycInfo Database Record (c) 2022 APA, all rights reserved).This reply to van IJzendoorn and Bakermans-Kranenburg (2022) debates the relevance of deinstitutionalization policies for children in alternative care. In view of coronavirus disease (COVID-19), climate change, and conflict, the gap between available solutions and numbers of children losing parental care is increasing. This challenge calls for innovative solutions to provide care. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Typical large-group institutions for abandoned children or orphans are known to be bad for the development of children, but what about small-group care? Rygaard (2020) presents SOS Children's Villages (SOSCV) as a natural and nondetrimental setting for abandoned children. In a random effects meta-analysis, we combined the scientific evidence on the physical and mental health of children growing up in SOSCV compared with peers growing up in typical institutions and in biological and foster families (N = 1,567). Results showed substantial developmental delays of SOSCV children compared with their peers in family care. Compared with children in typical institutions SOSCV children do better on mental health but even worse on physical growth. All efforts should be directed not to improving group care, but to the transition to family based care and the prevention of separation. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Krueger et al. (2022) argue that our review (Orth & Robins, 2022) finds benefits of self-esteem primarily for subjective outcomes and largely fails to demonstrate any "objective" benefits. We disagree with this portrayal of the findings and highlight research that provides evidence for the benefits of self-esteem using objective measures. We also address Krueger et al.'s claim that positivity bias in self-reports can account for the effects of self-esteem on subjectively assessed life outcomes, and explain how the statistical analyses used to document these effects substantially control for this bias. We maintain that there is now a large body of evidence from meta-analyses and large-scale longitudinal studies demonstrating that high self-esteem has adaptive consequences for social relationships, school, work, mental health, physical health, and antisocial behavior. Brummelman (2022) presents a compelling theoretical framework that can guide the design of interventions to improve children's self-esteem. We agree with his concerns about the need for randomized controlled trials to evaluate the efficacy of self-esteem interventions and the importance of ensuring that children's self-esteem can be raised without causing them to become narcissistic. The research reviewed in our article indicates that high self-esteem is adaptive for children, adolescents, and adults, suggesting that well-designed and effective self-esteem interventions might be beneficial for individuals of all ages. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Since the 1960s, self-esteem has become a cornerstone of Western child-rearing. After reviewing a large body of rigorous longitudinal research, Orth and Robins (2022) conclude that self-esteem brings modest but significant benefits across all ages. However, the authors did not intend to suggest strategies for raising children's self-esteem. The aim of my commentary is to identify such strategies. Without guidance on how to raise children's self-esteem safely and sustainably, well-intentioned strategies, such as inflated praise, may inadvertently undermine self-esteem or even breed narcissism. Instead, interventions should be based on a theoretically informed and empirically supported understanding of the determinants of self-esteem. By targeting these determinants, interventions may be able to raise children's self-esteem safely (i.e., without breeding narcissism) and sustainably (i.e., leading to lasting improvements in self-esteem and its presumed outcomes). Evaluating these interventions through randomized controlled trials will help build a theory of when and why self-esteem interventions work. Ultimately, this work will provide nuanced and dependable guidance to parents, teachers, and professionals on how to raise children's self-esteem. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Reviewing the literature of the past two decades, Orth and Robins (2022) conclude that high self-esteem yields reliable benefits. In this commentary, we caution that for objective outcome measures, these effects are variable- and domain-dependent. The allure of high self-esteem remains largely a matter of mind and memory, not behavior. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Debates about the benefits of self-esteem have persisted for decades, both in the scientific literature and in the popular press. Although many researchers and lay people have argued that high self-esteem helps individuals adapt to and succeed in a variety of life domains, there is widespread skepticism about this claim. The present article takes a new look at the voluminous body of research (including several meta-analyses) examining the consequences of self-esteem for several important life domains relationships, school, work, mental health, physical health, and antisocial behavior. Overall, the findings suggest that self-esteem is beneficial in all these domains, and that these benefits hold across age, gender, and race/ethnicity, and controlling for prior levels of the predicted outcomes and potential third variable confounds. The meta-analytic estimates of self-esteem effects (which average .10 across domains) are comparable in size to estimates for other hypothesized causal factors such as self-efficacy, positive emotionality, attachment security, and growth mindset, and larger than some generally accepted pharmaceutical interventions. Discussion focuses on several issues that are critical for evaluating the findings, including the strength of the evidence for making causal inferences, the magnitude of the effects, the importance of distinguishing between self-esteem and narcissism, and the generalizability of the results. In summary, the present findings support theoretical conceptions of self-esteem as an adaptive trait that has wide-ranging influences on healthy adjustment and adaptation, and suggest that interventions aimed at boosting self-esteem might, if properly designed and implemented, benefit individuals and society as a whole. (PsycInfo Database Record (c) 2022 APA, all rights reserved).In this editorial, the author gives voice to three principles that he hopes will influence the articles that appear in American Psychologist The scholarship should be rigorous, it should attend to both basic and applied considerations, and authors should be open and transparent in the reporting of how the research was conducted. The author says he would be remiss if he didn't also mention the importance of free and open inquiry. Progress in science depends on an atmosphere that permits-indeed, promotes-original thinking. A discipline, like psychology, that hopes to flourish by expanding the reach of its explanations must encourage divergent thinking and the thoughtful and respectful exchange of ideas while meeting criteria for excellent scholarship. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Memorializes Jack Michael (1926-2020). Michael, professor emeritus of Western Michigan University, was a pioneer in the field of behavior analysis and one of its most influential teachers. He was the recipient of numerous awards and honors including the Distinguished Teaching Award from the American Psychological Association (APA; 1971) and the Distinguished Service to Behavior Analysis Award from the Association for Behavior Analysis International (ABAI; 2002). Michael helped start ABAI, the largest organization of behavior analysts, in 1974. He was president of ABAI in 1979 and president of Division 25 (Behavior Analysis) of APA in 1983. Michael died November 12, 2020. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Recent evidence demonstrates rising self-oriented, other-oriented, and socially prescribed perfectionism among young people from the United States, United Kingdom, and Canada (Curran & Hill, 2019). One reason why perfectionism is increasing may be that rising competitiveness and individualism are requiring parents to engage in anxious, overly involved, and/or overly controlling forms of parenting. Yet, data to support this claim are limited and contested. In two meta-analyses, we expanded upon and tested this claim by examining whether excessive parental expectations and harsh parental criticism are correlated with perfectionism (Study 1) and whether these perceived practices are changing over time among American, Canadian, and British college students (Study 2). In Study 1, meta-analyses found small-to-moderate positive mean weighted effects of parental expectations and parental criticism on self-oriented and other-oriented perfectionism, and large positive mean weighted effects of parental expectations and parental criticism on socially prescribed perfectionism. In Study 2, using cross-temporal meta-analysis, we found that mean levels of parental expectations and parental criticism had linearly increased between 1989 and 2019 among college students. With rising competitiveness, individualism, economic inequality, and pressure to excel at school and college as the societal background, increases in parental expectations and parental criticism offer the most plausible explanation for rising perfectionism to date. (PsycInfo Database Record (c) 2022 APA, all rights reserved).A consistent finding in behavioral economics is that in social dilemma situations in which individuals must decide between individual and group welfare, cooperation declines over time eventually resulting in noncooperation. Extant theorizing addressing phenomena such as adaptive belief-learning focus solely on cognitive explanations. Based on the appraisal-tendency framework, we propose and show that the development of cooperation has a strong emotional component. Others' actual cooperative behavior compared to their expected cooperative behavior does not only result in adapting beliefs (cognition) but also gives rise to feelings of anger and guilt. These, in turn, drive individuals' subsequent cooperative behavior. Whereas experienced anger exacerbates the decline of cooperation, experienced guilt has a cushioning effect, potentially countering the progression toward noncooperation. Results also show differences in the emotional experience and resulting emotionally driven cooperation behavior between cooperative types. Particularly free riders tend to act on anger but not on guilt, shedding additional light on the emotionally driven role of free riders in the development of noncooperation. Finally, we find evidence for emotional carryover. Emotionally driven cooperation behavior is not limited to individuals causing the emotions, but is also transferred to individuals who are not directly responsible. Overall, the study provides further evidence for the appraisal and action tendency of anger and guilt and highlights the importance of emotions in repeated cooperative interactions. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Following the popularity of dual process models in social and cognitive psychology, there is major interest in the possibility that autism is associated with impaired "fast" intuitive thinking but enhanced "slow" or "rational" deliberative thinking. If correct, this has great potential to help understand various strengths and difficulties characteristic of autism. Previous empirical investigations of this phenomenon, however, are marred by concerns about the measurement of intuitive and deliberative processing, as well as broader problems in clinical psychological science (e.g., small underpowered studies, lack of replication). Making a step change, we conducted four large-scale studies to examine dual processing in autism, including a preregistered comparison of 200 autistic and nonautistic adults. Participants completed contemporary cognitive and self-report measures of intuitive and deliberative processing, as well as a psychometrically robust measure of general cognitive ability. Except for lower self-reported intuitive thinking, we found no unique contributions of autism to intuitive or deliberative thinking across all four studies, as evidenced by frequentist and Bayesian analyses. Overall, these studies indicate that intuitive and deliberative thinking is neither enhanced nor particularly impaired in relation to autism. We deliberate on the implications of these findings for theories of autism and future investigation of strengths and difficulties in autistic people. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Anxiety is defined as an anticipatory response to uncertain, future threats. It is unknown how anticipatory information regarding uncertainty about upcoming threatening and neutral stimuli impacts attention and perception in anxiety. Individuals with and without anxiety disorders performed two perceptual decision-making tasks in which they used threat or neutral prestimulus cues to discriminate between subsequent threatening and neutral faces. In one task, cues provided no probability information (high uncertainty). In the other, cues indicated a high probability of encountering threatening or neutral faces (low uncertainty). Under high uncertainty only, anxious apprehension was associated with worse discrimination between threatening versus neutral faces after threat cues. Additionally, anxious arousal was associated with worse discrimination after neutral cues in individuals with anxiety disorders. These findings will advance the field by spurring the development of more comprehensive and ecologically valid models in which anticipatory top-down factors influence threat perception in anxiety. (PsycInfo Database Record (c) 2022 APA, all rights reserved).Altered stress-reactivity may represent a general risk factor for psychopathology. In a broad at-risk sample, we examined (a) how stress and mild, daily expressions of psychopathology were interrelated over time, (b) whether we could detect subgroups with similar dynamics between stress and daily expressions of psychopathology (i.e., stress-reactivity), and (c) whether stress-reactivity was associated with psychopathology and social functioning. One hundred twenty-two young adults (43.4% women, mean age 23.6) at risk for developing a wide range of psychopathology completed a 6-month daily diary study. We used group iterative multiple model estimation (GIMME) to identify temporal associations between event stress and 11 mild expressions of psychopathology (e.g., feeling down, restlessness) at group, subgroup, and individual levels. Stress was associated with feeling irritated during the same day for >70% of individuals, and with feeling down and worrying during the same day for >50% of individuals. No stable subgroups characterized by similar daily stress-reactivity were identified. Instead, we observed 71 different stress-reactivity patterns in 122 individuals. Average daily event stress, but not overall stress-reactivity (weighted stress-response), was associated with psychopathology severity and social dysfunction. This study showed important similarities, as well as many differences between individuals, in terms of the impact of stress on mild expressions of psychopathology in daily life. Clustering based on similar stress-reactivity did not lead to stable subgroups. Finally, average daily stress levels, but not daily stress-reactivity, were associated with psychopathologic severity and social dysfunction. Findings highlight the importance of considering heterogeneity in stress-reactivity, but also challenges for identifying generalizable processes in doing so. (PsycInfo Database Record (c) 2022 APA, all rights reserved).A three-step process for the enantioselective assembly of cis-fused octahydrophenanthrenes with a quaternary stereocenter is reported. This synthetic strategy relies on a regioselective γ-alkylation, a one-pot sequence of asymmetric hydrogenation and oxidation, and an intramolecular enolate arylation to facilitate the rapid and enantioselective construction of cis-fused octahydrophenanthrene scaffolds with an arylated all-carbon quaternary stereocenter concisely and efficiently.Coherent coupling of defect spins with surrounding nuclei along with the endowment to read out the latter are basic requirements for an application in quantum technologies. We show that negatively charged boron vacancies (VB-) in hexagonal boron nitride (hBN) meet these prerequisites. We demonstrate Hahn-echo coherence of the VB- spin with a characteristic decay time Tcoh = 15 μs, close to the theoretically predicted limit of 18 μs for defects in hBN. Elongation of the coherence time up to 36 μs is demonstrated by means of the Carr-Purcell-Meiboom-Gill decoupling technique. Modulation of the Hahn-echo decay is shown to be induced by coherent coupling of the VB- spin with the three nearest 14N nuclei via a nuclear quadrupole interaction of 2.11 MHz. DFT calculation confirms that the electron-nuclear coupling is confined to the defective layer and stays almost unchanged with a transition from the bulk to the single layer.Herein, we report a distinctive photoredox/copper dual-catalyzed esterification of benzylic C-H bonds through the combination of photoredox-mediated hydrogen atom transfer and Cu(II)-mediated radical-polar crossover. This methodology demonstrates a high functional group tolerance (>40 examples) and moderate to good yields with structurally diverse benzylic C-H substrates. Notably, stoichiometric amounts of carboxylic acids are used as coupling partners, which allows the synthesis of structurally diverse benzylic esters and the late-stage functionalization of pharmaceuticals.We report the isolation of hydroxy mercapto methylene (HO-C̈-SH) under cryogenic conditions via pyrolysis of 2-ethoxy-2-thioxo-acetic acid. The two most stable carbene rotamers form via extrusion of ethylene and CO2 from this precursor. This donor-stabilized carbene represents a hitherto uncharacterized CH2SO species and the first spectroscopically characterized free mercapto carbene. CCSD(T)/cc-pVTZ computations support our findings.Recent breakthroughs in cell membrane-fabricated nanovaccine offer innovateive therapeutic options for preventing tumor metastasies and recurrence, yet the treatment of patient-specific solid tumor remained challenging owing to the immunosuppressive tumor microenvironment. Herein, we developed a personalized photothermal nanovaccine based on the surgical tumor-derived cell membranes (CMs) coating resiquimod (R848) loaded mesoporous polydopamine (MPDA) nanoparticles for targeting tumor photothermal immunotherapy and prevention. The fabricated photothermal nanovaccine MPDA-R848@CM (MR@C) demonstrates outstanding imaging-guided photothermal immunotherapy efficacy to eradicate solid tumors under near-IR laser irradiation and further inhibiting metastasis tumors by the resulted antitumor immunities, especially in combination with programmed death-ligand 1 antibody therapy (aPD-L1). Furthermore, from in vivo prophylactic testing results, it is confirmed that the 4T1 cells rechallenge can be prevented 100% in postsurgical tumor model after vaccination of the photothermal nanovaccine. Our work fabricates a personalized photothermal nanovaccine that possesses great potential for tumor-specific treatment and for preventing postoperative tumor recurrence.We herein report the first visible-light-mediated cross-coupling of unactivated alkyl iodides with aryl bromides through synergistic halogen atom transfer (XAT) and nickel catalysis. This simple protocol operates under mild reaction conditions and tolerates a variety of functional groups affording C(sp3)-C(sp2) cross-coupling products in good to moderate yields.Hybrid organic-inorganic perovskites [NH2NH3][X(HCOO)3] (X = Mn, Fe, Co) have a so-called "wine-rack" type of geometry that could give origin to the rare property of negative linear compressibility, which is an exotic and highly desirable material response. We use first-principles density functional theory computations to probe the response of these materials to hydrostatic pressure and predict that, indeed, all three of them exhibit negative linear compressibility above a critical pressure of 1 GPa. Calculations reveal that, under pressure, XO6 octahedra and -HCOO ligands remain relatively rigid while XO6 octahedra tilt significantly, which leads to highly anisotropic mechanical properties and expansion along certain directions. These trends are common for the three materials considered.This work delineates an integrative approach combining spectroscopic and computational studies to decipher the association-induced fluorescence properties of a fluorescent molecular rotor, viz., auramine O (AuO), after interacting with 20-mer duplex DNA having diverse well-matched base pairs. While exploring the scarcely explored sequence-dependent interaction mechanism of AuO and DNA, we observed that DNA could act as a conducive scaffold to the formation of AuO dimer through noncovalent interactions at lower molecular density. The photophysical properties of AuO depend on the nucleotide compositions as described from sequence-dependent shifting in the emission and absorption maxima. Furthermore, we explored such DNA base pair-dependent fluorescence spectral characteristics of AuO toward discriminating the thermodynamically most stable single nucleotide mismatch in a 20-mer sequence. Our results are interesting and could be useful in developing analogues with further enhanced emission properties toward mismatched DNA sequences.The desiccation of biofluid droplets leads to the formation of complex deposits which are morphologically affected by the environmental conditions, such as temperature. In this work, we examine the effect of substrate temperatures between 20 and 40 °C on the desiccation deposits of fetal bovine serum (FBS) droplets. The final dried deposits consist of different zones a peripheral protein ring, a zone of protein structures, a protein gel, and a central crystalline zone. We focus on the crystalline zone showing that its morphological and topographical characteristics vary with substrate temperature. The area of the crystalline zone is found to shrink with increasing substrate temperature. Additionally, the morphology of the crystalline structures changes from dendritic at 20 °C to cell-like for substrate temperatures between 25 and 40 °C. Calculation of the thermal and solutal Bénard-Marangoni numbers shows that while thermal effects are negligible when drying takes place at 20 °C, for higher substrate temperatures (25-40 °C), both thermal and solutal convective effects manifest within the drying drops. Thermal effects dominate earlier in the evaporation process leading, we believe, to the development of instabilities and, in turn, to the formation of convective cells in the drying drops. Solutal effects, on the other hand, are dominant toward the end of drying, maintaining circulation within the cells and leading to crystallization of salts in the formed cells. The cell-like structures are considered to form because of the interplay between thermal and solutal convection during drying. Dendritic growth is associated with a thicker fluid layer in the crystalline zone compared to cell-like growth with thinner layers. For cell-like structures, we show that the number of cells increases and the area occupied by each cell decreases with temperature. The average distance between cells decreases linearly with substrate temperature.Structure-based drug discovery (SBDD) largely relies on structural information from X-ray crystallography because traditional NMR structure calculation methods are too time consuming to be aligned with typical drug discovery timelines. The recently developed NMR molecular replacement (NMR2) method dramatically reduces the time needed to generate ligand-protein complex structures using published structures (apo or holo) of the target protein and treating all observed NOEs as ambiguous restraints, bypassing the laborious process of obtaining sequence-specific resonance assignments for the protein target. We apply this method to two therapeutic targets, the bromodomain of TRIM24 and the second bromodomain of BRD4. We show that the NMR2 methodology can guide SBDD by rationalizing the observed SAR. We also demonstrate that new types of restraints and selective methyl labeling have the potential to dramatically reduce "time to structure" and extend the method to targets beyond the reach of traditional NMR structure elucidation.The free radical cyclization reaction is a promising strategy for ring framework formation. Herein, we report a copper-catalyzed tandem radical cyclization strategy for preparing substituted lactam derivatives. This reaction proceeds through a radical coupling approach, which not only allows a wide range of alkenes but also is quite compatible with the primary, secondary, and tertiary radicals. In addition, density functional theory calculations were performed to gain insights into the reaction mechanism.Dihydroartemisinic acid (DHAA) is a plant natural product that undergoes a spontaneous endoperoxide-forming cascade reaction to yield artemisinin in the presence of air. The endoperoxide functional group gives artemisinin its biological activity that kills Plasmodium falciparum, the parasite that causes malaria. To enhance our understanding of the mechanism of this cascade reaction, 2,3-didehydrodihydroartemisinic acid (2,3-didehydro-DHAA), a DHAA derivative with a double bond at the C2-position, was synthesized. When 2,3-didehydro-DHAA was exposed to air over time, instead of forming an endoperoxide, this compound predominantly underwent aromatization. This olefinated DHAA analogue reveals the requirement of a monoalkene functional group to initiate the endoperoxide-forming cascade reaction to yield artemisinin from DHAA. In addition, this aromatization process was exploited to illustrate the autoxidation process of a different plant natural product, dihydroserrulatene, to form the aromatic ring in serrulatene. This spontaneous aromatization process has applications in other natural products such as leubethanol and erogorgiaene. Due to their similarity in structure to antimicrobial natural products, the synthesized compounds in this study were tested for biological activity. A group of the tested compounds had minimum inhibitory concentration (MIC) values ranging from 12.5 to 25 μg/mL against the bacterial pathogen Staphylococcus aureus and the fungal pathogen Cryptococcus neoformans.An interaction between methyl torsion and the low-lying out-of-plane methyl wag vibration has been observed in toluene, p-fluorotoluene, and m-fluorotoluene, contravening the traditional assumption used when analyzing spectra that methyl torsion can be treated independently of the small-amplitude vibrations. When a methyl group is attached to a planar frame, out-of-plane methyl wag vibrations always occur, and hence this type of interaction between methyl torsion and vibration is potentially extensive. To probe whether this coupling occurs beyond toluene and its derivatives, we have studied the far-infrared absorption band for the out-of-plane methyl wagging mode in N-methylpyrrole. The torsional sequence structure reveals a particularly strong torsion-vibration interaction. Spectral simulations yield a torsion-vibration coupling matrix element of 34.0 cm-1, over twice the value for toluene. The large torsion-vibration coupling constant implies that there is a significant tilting of the methyl group out of plane. Quantum chemistry calculations reveal a much larger out-of-plane methyl tilt angle in N-methylpyrrole compared to toluene, qualitatively consistent with this expectation. This is the first nontoluene derivative for which this type of torsion-vibration interaction has been reported and shows that the effect extends beyond toluenes. When present, this interaction links small-amplitude vibrations to the methyl torsion, providing a mechanism to bring the increased density of states into play and accelerate the rate of intramolecular vibrational energy redistribution.The nitrogenase active-site cofactor must accumulate 4e-/4H+ (E4(4H) state) before N2 can bind and be reduced. Earlier studies demonstrated that this E4(4H) state stores the reducing-equivalents as two hydrides, with the cofactor metal-ion core formally at its resting-state redox level. This led to the understanding that N2 binding is mechanistically coupled to reductive-elimination of the two hydrides that produce H2. The state having acquired 2e-/2H+ (E2(2H)) correspondingly contains one hydride with a resting-state core redox level. How the cofactor accommodates addition of the first e-/H+ (E1(H) state) is unknown. The Fe-nitrogenase FeFe-cofactor was used to address this question because it is EPR-active in the E1(H) state, unlike the FeMo-cofactor of Mo-nitrogenase, thus allowing characterization by EPR spectroscopy. The freeze-trapped E1(H) state of Fe-nitrogenase shows an S = 1/2 EPR spectrum with g = [1.965, 1.928, 1.779]. This state is photoactive, and under 12 K cryogenic intracavity, 450 nm photolysis converts to a new and likewise photoactive S = 1/2 state (denoted E1(H)*) with g = [2.009, 1.950, 1.860], which results in a photostationary state, with E1(H)* relaxing to E1(H) at temperatures above 145 K. An H/D kinetic isotope effect of 2.4 accompanies the 12 K E1(H)/E1(H)* photointerconversion. These observations indicate that the addition of the first e-/H+ to the FeFe-cofactor of Fe-nitrogenase produces an Fe-bound hydride, not a sulfur-bound proton. As a result, the cluster metal-ion core is formally one-electron oxidized relative to the resting state. It is proposed that this behavior applies to all three nitrogenase isozymes.Here, we report on a new kind of compound, XδIr4X12-δ (X = P, As), the first hole-doped skutterudites superconductor. We provide atomic-resolution images of the caging As atoms using scanning transmission electron microscopy (STEM). By inserting As atoms into the caged structure under a high pressure, superconductivity emerges with a maximum transition temperature (Tc) of 4.4 K (4.8 K) in IrAs3 (IrP3). In contrast to all of the electron-doped skutterudites, the electronic states around the Fermi level in XδIr4X12-δ are dominated by the caged X atom, which can be described by a simple body-centered tight-binding model, implying a distinct pairing mechanism. Our density functional theory (DFT) calculations reveal an intimate relationship between the pressure-dependent local-phonon mode and the enhancement of Tc. The discovery of XδIr4X12-δ provides an arena to investigate the uncharted territory of hole-doped skutterudites, and the method proposed here represents a new strategy of carrier doping in caged structures, without introducing extra elements.Maca is a protein-enriched edible plant with immunomodulatory activity. However, the role of proteins in the immunomodulatory activity of maca is unclear. In this study, peptide products of maca proteins obtained through in vitro gastrointestinal digestion were isolated and purified, and the immunomodulatory activities of these peptides were assessed in macrophages (RAW 264.7 cells). The results show that the maca protein hydrolysate enhanced the phagocytic capacity and NO, TNF-α, and IL-6 secretion of RAW 264.7 cells. Forty-five peptides from known proteins of maca or the cruciferous family were identified by ultraperformance liquid chromatography-tandem mass spectrometry in the hydrolysate, and the peptide RNPFLP exhibited the strongest immunomodulatory activity. Antibody blocking, siRNA, pathway inhibitors, and western blot assays showed that RNPFLP-activated RAW 264.7 cells through the NF-κB and MAPK signaling pathways mediated by TLR2 and TLR4 receptors. An analysis of the structure-activity relationship showed that the N9-H60 active site in arginine plays an important role in the immunomodulatory activity of RNPFLP. This study provides a new understanding of the immunomodulatory activity of maca.Intensive applications of toxic malathion pesticides bring a vital threat to the environment and health. Hence, a credible and sensitive strategy is urgently needed for the respective detection of malathion. In this work, an aptamer-based nonenzymatic autonomous DNA walking machine was fabricated for monitoring trace malathion contamination in cells and foods. Along with the machine walking driven by malathion-triggered reaction entropy, multiple fluorescent signal outputs were thermodynamically generated for signal amplification. The proposed stable DNA nanomachine achieved satisfactory results with a detection limit of 81.9 pg L-1 for testing malathion, which could be applied to actual samples including apple juice, paddy water, and paddy soil. Furthermore, the high stability, sensitivity, and biocompatibility of the nanomachine enabled monitoring of the malathion contamination in living cells and bioaccumulation in lettuce without additional purification. Consequently, with these excellent performances, it is strongly anticipated that the DNA walking machine has tremendous potential to be extended to general platforms against pesticides to avoid malathion-contaminated agricultural production for environmental safety and human health.Developing probes to simultaneously detect and discriminate biothiols is important, yet challenging. Activatable photoacoustic (PA) probes for discriminating biothiols in vivo are still lacking, and this hinders the diagnosis of thiol-related diseases. Herein we present the first PA and fluorescence dual-modality probe MB-NBD for discriminating different biothiol species. The probe has the advantages of both fluorescence imaging and PA imaging (high sensitivity and deep penetration) with distinct signal patterns toward hydrogen sulfide (H2S), cysteine/homocysteine (Cys/Hcy), and glutathione (GSH) treatment. The biothiol-activated product of MB-NBD exhibits enhancements in near-infrared fluorescence (NIRF) at 690 nm and absorbance/PA at 664 nm upon fast reaction, allowing it to selectively detect biothiol species over other reactive species. On the other hand, MB-NBD displays characteristic absorbance enhancement at 547 nm toward H2S, rendering specific detection of H2S. In addition, the specific enhancements in absorbance/PA at 470 nm and fluorescence at 550 nm toward Cys/Hcy treatment endows the probe with the capability of selectively detecting Cys/Hcy. Furthermore, MB-NBD is able to discriminate Cys and GSH by fluorescent imaging in live-cell and ratiometric PA imaging in mice experiments. MB-NBD has been successfully used to diagnose tumors by dual-channel ratiometric PA imaging.Biosynthesis has been a diverse toolbox to develop bioactive molecules and materials, especially for fabricating modified peptides and their assemblies induced by enzymes. Although desired chemical structures and nanoarchitectures have been achieved, the subsequent interferences of peptide assemblies with organelles and the cellular pathways still remain unsolved important challenges. Herein, we developed a new tripeptide, phenylalanine-phenylalanine-tyrosine (Phe-Phe-Tyr, or FFY), which can be intracellularly oxidized and in situ self-assemble into nanoparticles with excellent interference capability with microtubules and ultimately reverse the drug resistance of melanoma. With the catalysis of tyrosinase, FFY was first oxidized to a melanin-like FFY dimer (mFFY) with a diquinone structure for further self-assembling into mFFY assemblies, which could inhibit the self-polymerization of tubulin to induce severe G2/M arrest (13.9% higher than control). Afterward, mitochondrial dysfunction was also induced for overproduction of cleaved caspase 3 (3.1 times higher than control) and cleaved PARP (6.3 times higher), achieving a high level of resistant reversing without chemotherapeutic drugs. In vivo studies showed that the resistant melanoma tumor volumes were reduced by 87.4% compared to control groups after FFY treatment by peritumoral injections. Overall, this tyrosinase-induced tripeptide assembly has been demonstrated with effective intrinsic apoptosis against drug-resistant melanoma, providing a new insight into utilizing biomolecules to interfere with organelles to activate certain apoptosis pathways for treatment of drug-resistant cancer.RNA is dynamically modified in cells by a plethora of chemical moieties to modulate molecular functions and processes. Over 140 modifications have been identified across species and RNA types, with the highest density and diversity of modifications found in tRNA (tRNA). The methods used to identify and quantify these modifications have developed over recent years and continue to advance, primarily in the fields of next-generation sequencing (NGS) and mass spectrometry (MS). Most current NGS methods are limited to antibody-recognized or chemically derivatized modifications and have limitations in identifying multiple modifications simultaneously. Mass spectrometry can overcome both of these issues, accurately identifying a large number of modifications in a single run. Here, we present advances in MS data acquisition for the purpose of RNA modification identification and quantitation. Using this approach, we identified multiple tRNA wobble position modifications in Arabidopsis thaliana that are upregulated in salt-stressed growth conditions and may stabilize translation of salt stress induced proteins.