A new perspective on individual reliability beyond group effect for event-related potentials: A multisensory investigation and computational modeling.

The dominant approach in investigating the individual reliability for event-related potentials (ERPs) is to extract peak-related features at electrodes showing the strongest group effects. Such a peak-based approach implicitly assumes ERP components showing a stronger group effect are also more reliable, but this assumption has not been substantially validated and few studies have investigated the reliability of ERPs beyond peaks. In this study, we performed a rigorous evaluation of the test-retest reliability of ERPs collected in a multisensory and cognitive experiment from 82 healthy adolescents, each having two sessions. By comparing group effects and individual reliability, we found that a stronger group-level response in ERPs did not guarantee higher reliability. A perspective of neural oscillation should be adopted for the analysis of reliability. Further, by simulating ERPs with an oscillation-based computational model, we found that the consistency between group-level ERP responses and individual reliability was modulated by inter-subject latency jitter and inter-trial variability. The current findings suggest that the conventional peak-based approach may underestimate the individual reliability in ERPs and a neural oscillation perspective on ERP reliability should be considered. Hence, a comprehensive evaluation of the reliability of ERP measurements should be considered in individual-level neurophysiological trait evaluation and psychiatric disorder diagnosis.

Multi Scale Ethics-Why We Need to Consider the Ethics of AI in Healthcare at Different Scales.

Many researchers have documented how AI and data driven technologies have the potential to have profound effects on our lives-in ways that make these technologies stand out from those that went before. Around the world, we are seeing a significant growth in interest and investment in AI in healthcare. This has been coupled with rising concerns about the ethical implications of these technologies and an array of ethical guidelines for the use of AI and data in healthcare has arisen. Nevertheless, the question of if and how AI and data technologies can be ethical remains open to debate. This paper aims to contribute to this debate by considering the wide range of implications that have been attributed to these technologies and asking whether current ethical guidelines take these factors into account. In particular, the paper argues that while current ethics guidelines for AI in healthcare effectively account for the four key issues identified in the ethics literature (transparency; fairness; responsibility and privacy), they have largely neglected wider issues relating to the way in which these technologies shape institutional and social arrangements. This, I argue, has given current ethics guidelines a strong focus on evaluating the impact of these technologies on the individual, while not accounting for the powerful social shaping effects of these technologies. To address this, the paper proposes a Multiscale Ethics Framework, which aims to help technology developers and ethical evaluations to consider the wider implications of these technologies.

Trade-offs between weapons and testes do not manifest at high social densities.

Social conditions can alter the allocation of resources to reproductive traits. For example, an increase in social density during development is frequently associated with an increase in the testes mass of males. Sperm competition theory assumes that increased investment in testes should come at the expense of investing into precopulatory traits, such as sexually selected weaponry. However, much remains unknown about the role of the social context on the concurrent, relative investment in both testes and weapons. We found that the leaf-footed cactus bug, Narnia femorata (Hemiptera: Coreidae), grew nearly 20% larger testes when raised in high social densities. In addition to manipulating social density, we used autotomy (limb loss) to limit investment in their hindlimb weapon during development. At low densities, we found that those that lost a weapon during development grew larger testes by adulthood, supporting previous work demonstrating a weapons-testes trade-off. However, at high social densities, males that dropped a hindlimb did not grow larger testes, though testes were already large at this density. These results underscore the importance of the social context to resource allocation patterns within the individual.

Intermolecular Heck Coupling with Hindered Alkenes Directed by Potassium Carboxylates.

Pd0 -catalyzed Mizoroki-Heck reactions traditionally exhibit poor reactivity with polysubstituted, unbiased alkenes. Intermolecular reactions with simple, all-carbon tetrasubstituted alkenes are unprecedented. Herein we report that pendant carboxylic acids, combined with bulky monophospine ligands on palladium, can direct the arylation of tri- and tetrasubstituted olefins. Quaternary carbons are established at high Fsp3 attached-ring junctures and the carboxylate directing group can be removed after coupling. Carboxylate directivity prevents over-arylation of the new, less substituted alkene, which can be diversified in subsequent reactions.

Amide Neighbouring-Group Effects in Peptides: Phenylalanine as Relay Amino Acid in Long-Distance Electron Transfer.

In nature, proteins serve as media for long-distance electron transfer (ET) to carry out redox reactions in distant compartments. This ET occurs either by a single-step superexchange or through a multi-step charge hopping process, which uses side chains of amino acids as stepping stones. In this study we demonstrate that Phe can act as a relay amino acid for long-distance electron hole transfer through peptides. The considerably increased susceptibility of the aromatic ring to oxidation is caused by the lone pairs of neighbouring amide carbonyl groups, which stabilise the Phe radical cation. This neighbouring-amide-group effect helps improve understanding of the mechanism of extracellular electron transfer through conductive protein filaments (pili) of anaerobic bacteria during mineral respiration.

Chemical Glucosylation of Labile Natural Products Using a (2-Nitrophenyl)acetyl-Protected Glucosyl Acetimidate Donor.

The synthesis of (2-nitrophenyl)acetyl (NPAc)-protected glucosyl donors is described that were designed for the neighboring-group assisted glucosylation of base-labile natural products also being sensitive to hydrogenolysis. Glycosylation conditions were optimized using a trichloroacetimidate glucosyl donor, and cyclohexylmethanol and (+)-menthol as model acceptors. The approach was then extended to a one-pot procedure for the synthesis of 1,2-trans-glycosides. This method was finally applied for improved synthesis of the masked mycotoxin T2-O-ß,d-glucoside.

Is being a "small fish in a big pond" bad for students´ psychosomatic health? A multilevel study on the role of class-level school performance.

BACKGROUND: Features of schools and classes are closely related to students´ health and wellbeing. However, class composition (e.g. in terms of school performance) has rarely been examined in relation to students´ health and wellbeing. This study focuses on the so called Big-Fish-Little-Pond-Effect (BFLPE), by investigating whether the level of high-performing students in classroom is negatively associated with psychosomatic complaints of students who perceive themselves as poor performers. METHODS: Data were derived from the German sample of the WHO-Collaborative "Health Behaviour in School-aged Children (HBSC)" study 2013/2014. The sample included 5226 11-, 13- and 15-year-old students. Individual perceived school performance (PSP) was included (very good/good vs. average/below average PSP) at the individual student-level. At the class-level, school performance in class was generated by aggregating the share (in percentage) of students who report a very good/good PSP to the class-level, indicating the percentage of students with good/very good PSP in classroom. Using multilevel regression models, the association between class-level school performance (in percentage of students with very good/good PSP) and individual psychosomatic complaints were analyzed, stratified by students´ individual PSP. RESULTS: Students who report average/below average PSP showed higher likelihoods of psychosomatic complaints (Odds Ratio: 1.75; 95% Confidence Interval: 1.52-2.03) compared to counterparts with very good/good PSP. The aggregated class-level PSP was not significantly associated with psychosomatic complaints. However, in line with the BFLPE, results further revealed that students with average/below average PSP, who attend classes with a higher percentage of students who report very good/good PSP, had higher likelihoods of psychosomatic complaints (Odds Ratio: 1.91; 95% Confidence Interval: 1.01-4.01) compared to classmates with very good/good PSP. CONCLUSIONS: This study revealed that class composition in terms of PSP was differentially associated with students´ psychosomatic complaints, depending on their individual PSP. Findings highlight the vulnerability of students with poor PSP placed in classes with a higher percentage of students with good PSP. Results of this study therefore indicate a need for initiatives for low performing students from teachers and school staff in class.

Fluorine in a C-F Bond as the Key to Cage Formation.

Cage molecules have long been employed to trap reactive or transient species, as their rigid nature allows them to enforce situations that otherwise would not persist. In this Minireview, we discuss our use of rigid cage structures to investigate the close noncovalent interactions of fluorine with other functional groups and determine how mutual proximity affects both physical properties and reactivity. Unusual covalent interactions of fluorine are also explored: the cage can close to form the first solution-phase C-F-C fluoronium ion.

Reductive Carbocyclization of Homoallylic Alcohols to syn-Cyclobutanes by a Boron-Catalyzed Dual Ring-Closing Pathway.

The organoborane-catalyzed reductive carbocyclization of homoallylic alcohols has been developed by using hydrosilanes as reducing reagents to provide a range of 1,2-disubstituted arylcyclobutanes. The reaction proceeds in a cis-selective manner with high efficiency under mild conditions. Mechanistic studies, including deuterium scrambling and Hammett studies, and DFT calculations, suggest a dual ring-closing pathway.

C3 -Symmetric Tricyclo[2.2.1.02,6 ]heptane-3,5,7-triol.

A straightforward access to a hitherto unknown C3 -symmetric tricyclic triol both in racemic and enantiopure forms has been developed. Treatment of 7-tert-butoxynorbornadiene with peroxycarboxylic acids provided mixtures of C1 - and C3 -symmetric 3,5,7-triacyloxynortricyclenes via transannular π-cyclization and replacement of the tert-butoxy group. By refluxing in formic acid, the C1 -symmetric esters were converted to the C3 -symmetric formate. Hydrolysis gave diastereoisomeric triols, which were separated by recrystallization. Enantiomer resolution via diastereoisomeric tri(O-methylmandelates) delivered the target triols on a gram scale. The pure enantiomers are useful as core units of dopants for liquid crystals.

Stereoselective ß-Mannosylation by Neighboring-Group Participation.

The stereoselective synthesis of glycosidic bonds is the main challenge of oligosaccharide synthesis. Neighboring-group participation (NGP) of C2 acyl substituents can be used to provide 1,2-trans-glycosides. Recently, the application of NGP has been extended to the preparation of 1,2-cis-glycosides with the advent of C2 chiral auxiliaries. However, this methodology has been strictly limited to the synthesis of 1,2-cis-gluco-type sugars. Reported herein is the design and synthesis of novel mannosyl donors which provide 1,2-cis-mannosides by NGP of thioether auxiliaries. A key element in the design is the use of (1) C4 locked mannuronic acid lactones to enable NGP of the C2 auxiliary. In addition to C2 participation a new mode of remote participation of the C4 benzyl group was identified and provides 1,2-cis-mannosides.

Amino-functionalized (meth)acryl polymers by use of a solvent-polarity sensitive protecting group (Br-t-BOC).

We describe the synthesis of bromo-tert-butyloxycarbonyl (Br-t-BOC)-amino-protected monomers 2-((1-bromo-2-methylpropan-2-yl)oxycarbonylamino)ethyl (meth)acrylate 3a,b. For this purpose, 2-isocyanatoethyl (meth)acrylate 1a,b was reacted with 1-bromo-2-methylpropan-2-ol (2a). The free radical polymerization of (Br-t-BOC)-aminoethyl (meth)acrylates 3a,b yielded poly((Br-t-BOC)-aminoethyl (meth)acrylate) 6a,b bearing protected amino side groups. The subsequent solvolysis of the Br-t-BOC function led to the new polymers poly(2-aminoethyl (meth)acrylate) 8a,b with protonated free amino groups. The monomers and the resulting polymers were thoroughly characterized by (1)H NMR, IR, GPC and DSC methods. The kinetics of the deprotection step was followed by (1)H NMR spectroscopy. The solvent polarity and neighboring group effects on the kinetics of deprotection are discussed.

Enhancement of neighbouring-group participation in Cu0-promoted cross-coupling gem-difluoromethylenation of aryl/alkenyl halides with 1,3-azolic difluoromethyl bromides.

A copper(0)-promoted direct reductive gem-difluoromethylenation of unactivated aryl or alkenyl halides with benzo-1,3-azolic (oxa-, thia- or aza-) difluoromethyl bromides or 2-bromodifluoromethyl-1,3-oxazoline has been developed for the construction of pharmaceutically important gem-difluoromethylene-linked twin molecules. The unique π-conjugated aryl-fused 1,3-azolic moiety in difluoromethyl bromide substrates could stabilise the reaction intermediates, which promotes the reactivities, providing facile access to the cross-coupling products in good to excellent yields, and allowing significant functional group tolerance. The reaction exhibits an enhanced neighbouring-group-participation effect. This method could provide a new strategy for the construction of gem-difluoromethylene-linked identical or nonidentical twin drugs through further functionalisation of 1,3-azolic skeletons.

Effects of Reference Group Instructions on Big Five Trait Scores.

People responding to personality questionnaires rate themselves by comparing themselves to some reference group, but this reference group is typically not specified. In this study, we examined the differences between Big Five trait scores when people responded to trait questionnaires without a specified reference group, as is typical in personality assessment, and when they were asked to compare themselves to people in general, close others, people their age, people their same gender, their ideal self, or their past self. We found that personality scores tended to be more adaptive for between-person comparisons than for within-person comparisons. We also found that unprompted instructions produced mildly higher scores across all traits. There were few differences among between-person reference group conditions. Men rated themselves as slightly more agreeable when comparing themselves to other men. Implications for basic and applied personality assessment are discussed.

Aggregations reduce winter metabolic rates in the diapausing ladybeetle Hippodamia convergens.

Energy conservation is linked to survival and fitness of overwintering ectotherms, and is particularly critical in winter. Although many insects overwinter individually, some form aggregations with conspecifics. Aggregations cause metabolic suppression in some insects, but the effect of aggregations on metabolic rates and energy use in overwintering aggregations remains underexplored. The convergent ladybeetle (Hippodamia convergens) overwinters in massive aggregations, making it an ideal system for testing the effect of aggregation size on metabolic rates in overwintering insects. We measured metabolic rates of beetle aggregations of 1, 10, 25, and 50 individuals using stop-flow respirometry across two ecologically relevant temperatures, and measured locomotor activity as one possible driver of group effects on metabolic rate. Metabolic rates per beetle decreased with increasing aggregation size at both temperatures, but was more pronounced at low temperatures. Metabolic rates scaled hypometrically with mass, with deeper response at cool temperatures. Activity decreased with aggregation size, but only at low temperatures. These results suggest that individuals within aggregations enter a deeper metabolically inactive state that single individual beetles cannot achieve, which is partly but not completely explained by a reduction in locomotor activity. This group strategy for energy conservation may provide an additional selective advantage for the evolution of large overwintering aggregations.

Healable, Recyclable, and Programmable Shape Memory Organogels Based on Highly Malleable Catalyst-Free Carboxylate Linkages.

The development of healable and recyclable organogels possessing responsive abilities is mainly hindered by the unavailability of many dynamic covalent linkages that undergo exchange reaction below the boiling temperature of organic swelling medium. Furthermore, the exchange is desired to be effective under catalyst-free conditions to circumvent the issue of catalyst leaching during the swelling process. Especially, imparting swift reversibility to thermostable carboxylate linkages is challenging. In this approach, we have utilized the ß-keto anchimeric assistance as the tool to induce swift reversibility into the conventional carboxylate linkage under mild temperature (∼70-90 °C) and catalyst-free conditions. Using this ß-keto carboxylate linkage as an associative bond exchange mean, strong (tensile strength = 0.3 MPa) and stretchable (ultimate elongation ≈ 600%) covalent adaptable organogels (CAOs) with anisotropic swelling, remoldable, self-healing, and shape memory ability are derived from commercially available precursors. The shape memory ability of these samples shows dependency on the shape fixing time and can be programmed, targeting further applications. Soft actuators may be fabricated from the CAOs using temperature and solvent as the activating tools. This research demonstrates that the conventional carboxylate linkages can be made labile under mild conditions for further applications.

Persuasive Technologies and Social Interactions in Professional Environments: Embedded Qualitative Case Study.

BACKGROUND: Although previous studies have highlighted the impact of interactions on the web in the context of patient-health care professional (HCP) dyads, this paper extends that context to a triad that includes the role of employers and associated settings with social groups. OBJECTIVE: This study aims to evaluate how the interactions between individuals and the social use of the platform affect individuals' use of persuasive technology and, in turn, their work environment actions and responses, by implementing a persuasive technology health and wellness platform in a work environment. METHODS: For 8 months, we deployed a persuasive technology platform with different combinations of health-related features and content in 1 embedded case design with 8 fire stations for a small Canadian city (total number of participant firefighters, n=141) assigned to 1 of 2 treatments-interactive or static webpages. We used text-based content analysis techniques for outcome measures, drawn from a total of 29 participant exit interviews. In addition, medical assessments were conducted at baseline, midpoint, and end point by 7 HCPs and 1 researcher (BM), who also served as the data steward and managed the study. RESULTS: Our results reveal that group, social, and work influences introduce new elements to the use of persuasive technology, which interact to foster higher levels of individual success. The platform in our study served as part of a larger social system, providing information that facilitated new behaviors at work and home. The 8-month group programs centered on exercise, nutrition, and smoking cessation. Groups of participants coached by certified professionals showed significant increases in sodium awareness, levels of actual exercise, and consistency of activities. As a result of the study, of 141 people, 15 (10.6%) were notified of serious medical health issues and 29 (20.6%) underwent blood work assessments and a privacy shield (protected by federal law) was enacted to protect employees from losing their employment based on any health concerns disclosed. CONCLUSIONS: The persuasive technology platform, in combination with self-management and professional management and social interactions, significantly altered work management behaviors. Interactions among individual outcomes, group influences, and social situations strongly influenced individuals' behaviors in their work and home environments. Three things further improved the positive results that we observed: privacy shields (which allowed employees to reveal health concerns without fear of professional consequences), individual private activities aligned with group activities, and integration between HCP work with localized, organizational work roles.

The Potential Influence of Group Membership on Outcomes in Indicated Cognitive-Behavioral Adolescent Depression Prevention.

BACKGROUND: Adolescent depression prevention programs are typically delivered in groups in which adolescents share a common setting and interventionist, but the influence of the group is usually ignored or statistically controlled. We tested whether the primary outcomes of reductions in depressive symptoms and future onset of major depressive disorder (MDD) varied as a function of group membership. METHODS: Data were available from two randomized trials in which 220 adolescents received the Blues Program indicated prevention intervention in 36 separate groups; participants were assessed at baseline, post intervention, and at 6-, 12-, and 24-month follow-ups. RESULTS: Ten percent of participants had developed MDD 2 years post intervention. Group-level effects for MDD onset over follow-up were nonsignificant (accounted for <1% of variance; ICC = 0.004, ns). Group-level effects for depressive symptom change across the follow-up period were also nonsignificant (ICC = 0.001, ns) but group effects accounted for 16% of depressive symptom change immediately post intervention (ICC = 0.159, p < 0.05). Group-level clustering of posttest depressive symptoms was not associated with size of group or gender composition. CONCLUSIONS: Membership in specific adolescent cognitive-behavioral depression prevention groups may have an impact in terms of immediate symptom reduction but does not appear to have significant prevention effects in terms of long-term symptom change or MDD onset.

Our Robots, Our Team: Robot Anthropomorphism Moderates Group Effects in Human-Robot Teams.

Past research indicates that people favor, and behave more morally toward, human ingroup than outgroup members. People showed a similar pattern for responses toward robots. However, participants favored ingroup humans more than ingroup robots. In this study, I examine if robot anthropomorphism can decrease differences between humans and robots on ingroup favoritism. This paper presents a 2 × 2 × 2 mixed-design experimental study with participants (N = 81) competing on teams of humans and robots. I examined how people morally behaved toward and perceived players depending on players' Group Membership (ingroup, outgroup), Agent Type (human, robot), and Robot Anthropomorphism (anthropomorphic, mechanomorphic). Results replicated prior findings that participants favored the ingroup over the outgroup and humans over robots-to the extent that they favored ingroup robots over outgroup humans. This paper also includes novel results indicating that patterns of responses toward humans were more closely mirrored by anthropomorphic than mechanomorphic robots.

Dative Directing Group Effects in Ti-Catalyzed [2+2+1] Pyrrole Synthesis: Chemo- and Regioselective Alkyne Heterocoupling.

Transient dative substrate-Ti interactions have been found to play a key role in controlling the regioselectivity of alkyne insertion and [2+2] cycloaddition in Ti-catalyzed [2+2+1] pyrrole synthesis and Ti-catalyzed alkyne hydroamination. TMS-protected alkynes with pendent Lewis basic groups can invert the regioselectivity of TMS-protected alkyne insertion, leading to the selective formation of highly substituted 3-TMS pyrroles. The competency of various potential directing groups was investigated, and it was found that the directing-group effect can be tuned by modifying the catalyst Lewis acidity, the directing-group basicity, or the directing-group tether length. Dative directing-group effects are unexplored with Ti catalysts, and this study demonstrates the potential power of dative substrate-Ti interactions in tuning selectivity.