Atomically Precise Au24Pt(thiolate)12(dithiolate)3 Nanoclusters with Excellent Electrocatalytic Hydrogen Evolution Reactivity.

[Au24Pt(C6)18]0 (C6 = 1-hexanethiolate) is twice as active as commercial Pt nanoparticles in promoting the electrocatalytic hydrogen evolution reaction (HER), thereby attracting attention as new HER catalysts with well-controlled geometric structures. In this study, we succeeded in synthesizing two new Au-Pt alloy nanoclusters, namely, [Au24Pt(TBBT)12(TDT)3]0 (TBBT = 4-tert-butylbenzenethiolate; TDT = thiodithiolate) and [Au24Pt(TBBT)12(PDT)3]0 (PDT = 1,3-propanedithiolate), by exchanging all the ligands of [Au24Pt(PET)18]0 (PET = 2-phenylethanethiolate) with mono- or dithiolates. Although [Au24Pt(TBBT)12(TDT)3]0 was synthesized serendipitously, a similar cluster, [Au24Pt(TBBT)12(PDT)3]0, was subsequently obtained by selecting the appropriate reaction conditions and optimal combination of thiolate and dithiolate ligands. Single crystal X-ray diffraction analyses revealed that the lengths and orientations of -Au(I)-SR-Au(I)- staples in [Au24Pt(TBBT)12(TDT)3]0 and [Au24Pt(TBBT)12(PDT)3]0 were different from those in [Au24Pt(C6)18]0, [Au24Pt(PET)18]0, and [Au24Pt(TBBT)18]0, and these subtle differences were reflected in the geometric and electronic structures as well as the HER activities of [Au24Pt(TBBT)12(TDT)3]0 and [Au24Pt(TBBT)12(PDT)3]0. Accordingly, the HER activities of products [Au24Pt(TBBT)12(TDT)3]0 and [Au24Pt(TBBT)12(PDT)3]0 were, respectively, 3.5 and 4.9 times higher than those of [Au24Pt(C6)18]0 and [Au24Pt(TBBT)18]0.

How people evaluate individuals who act morally prior to acting immorally: An examination of developmental change in moral evaluation, social preference, and prediction of moral behaviors.

Recent studies have enthusiastically examined the developmental origin of moral self-licensing, which is a tendency to act immorally after acting morally. However, it has not been considered enough how children evaluate personality traits of individuals who show moral licensing behavior and whether there is any developmental change in this evaluation. This study examined the developmental change in moral evaluation, social preference, and prediction of moral behaviors for moral licensing characters as well as moral or immoral characters. In total, 36 5- and 6-year-old children, 36 7- and 8-year-old children, and 58 university students participated in the study. The results revealed that 7- and 8-year-olds and adults evaluated moral licensing characters as more moral and likable than those who behave immorally, unlike 5- and 6-year-olds, who did not distinguish between the immoral and moral licensing characters. Importantly, 7- and 8-year-olds judged the moral licensing character as neutral in both moral evaluation and judgment of social preference, suggesting that they thought the immoral behavior was canceled out owing to prior moral behavior in the moral licensing character. However, adults still judged the moral licensing character as immoral and dislikable. Moreover, children's prediction of moral behavior for all characters showed the same tendency as moral evaluation, whereas adults' prediction was slightly different from their moral evaluation. Taken together, our findings revealed that the evaluation of individuals who show moral licensing behavior changed developmentally, and a moral licensing effect was found when evaluating others' moral traits from around 7 or 8 years of age.

Observing inefficient action can induce infant preference and learning.

'Motionese' can be defined as an exaggerated and repetitive action. It induces preference and learning in infants. However, which action component of motionese promotes infants' preference and learning remains largely unknown. In this study, we focused on inefficiency and toward-ness of action. Our study demonstrates that observing an inefficient holding out action can induce a visual preference in 4-month-old infants and learning in 10-month-old infants through eight experiments (N = 192). We found that when infants observe inefficient holding out action, the action attracts their attention and facilitates learning about the identity of the toy object accompanying it, especially when people direct inefficient actions towards them. Our findings indicate that both action efficiency and toward-ness may be key factors in infant learning.

[Ag23Pd2(PPh3)10Cl7]0: A new family of synthesizable bi-icosahedral superatomic molecules.

Icosahedral noble-metal 13-atom nanoclusters (NCs) can form connected structures, which can be regarded as superatomic molecules, by vertex sharing. However, there have been very few reports on the superatomic molecules formed using silver (Ag) as the base element. In this study, we synthesized [Ag23Pd2(PPh3)10Cl7]0 (Pd = palladium, PPh3 = triphenylphosphine, Cl = chloride), in which two icosahedral 13-atom NCs are connected, and elucidated its geometric and electronic structures to clarify what type of superatomic molecules can be synthesized. The results revealed that [Ag23Pd2(PPh3)10Cl7]0 is a synthesizable superatomic molecule. Single crystal x-ray diffraction analysis showed that the metal-metal distances in and between the icosahedral structures of [Ag23Pd2(PPh3)10Cl7]0 are slightly shorter than those of previously reported [Ag23Pt2(PPh3)10Cl7]0, whereas the metal-PPh3 distances are slightly longer. On the basis of several experiments and density functional theory calculations, we concluded that [Ag23Pd2(PPh3)10Cl7]0 and previously reported [Ag23Pt2(PPh3)10Cl7]0 are more stable than [Ag25(PPh3)10Cl7]2+ because of their stronger superatomic frameworks (metal cores). These findings are expected to lead to clear design guidelines for creation of new superatomic molecules.

Developmental process of the understanding of linguistic register in children: A comparison of typically developing children, autistic children, and children with Williams syndrome.

Although the developmental process of linguistic register-the appropriate manner of speech as determined by the listener and social situation-has been gradually clarified in typically developing (TD) children, research on the mechanism and developmental process of register acquisition in atypically developing children are insufficient. This study compared the developmental process of understanding linguistic register among TD children, autistic children, and those with Williams syndrome (WS), and examined the contributions of social cognition and motivation to the acquisition of linguistic register. Two experiments were designed to assess the recognition of which linguistic register to use when communicating with different listeners and of the listener's feelings according to the speakers' use of register. The results revealed that the process of understanding register-listener associations was nearly identical among all groups of children and their understanding improved with age. Conversely, their understanding of the effect of register selection on the listener's feelings varied. Importantly, as TD children mature, they become aware that adult listeners may feel negatively when spoken to in an inappropriate register, whereas autistic children and those with WS do not exhibit the same awareness. Thus, our results suggest that atypical social cognition and motivation do not disturb the understanding of register-listener associations. However, social cognition and motivation play important roles in understanding the effect of register selection on the listener's feelings. These findings provide a significant contribution to clarifying the mechanism of linguistic register acquisition.

Comparison of the Sensory Profile Among Autistic Individuals and Individuals with Williams Syndrome.

PURPOSE: With the current study, we aimed to reveal the similarities and differences in sensory profiles between Williams syndrome (WS) and autism spectrum disorder. METHODS: Using the sensory profile questionnaire completed by the caregivers, we analyzed the WS (n = 60, 3.4-19.8 years) and autistic (n = 39, 4.2-14.0 years) groups. RESULTS: The Severity Analysis revealed a significant group difference in Sensory Sensitivity but not in Low Registration, Sensation Seeking, and Sensation Avoiding subscales. Age can modulate the subscale scores differently across groups. For Sensation Seeking, the scores of both groups decreased with development. However, the scores of Sensory Sensitivity decreased with age in the autistic group but not in the WS group. Sensation Avoiding scores increased with development in the WS group but not in the autistic group. No significant developmental changes were observed in Low Registration. CONCLUSION: This study highlights the cross-syndrome similarities and differences in sensory profiles and developmental changes in autistic individuals and individuals with WS.

Characteristics of nobiletin-mediated alteration of gene expression in cultured cell lines.

Nobiletin, a polymethoxylated flavonoid that is highly contained in the peels of citrus fruits, exerts a wide variety of beneficial effects, including anti-proliferative effects in cancer cells, repressive effects in hyperlipidemia and hyperglycemia, and ameliorative effects in dementia at in vitro and in vivo levels. In the present study, to further understand the mechanisms of these actions of nobiletin, the nobiletin-mediated alterations of gene expression in three organ-derived cell lines - 3Y1 rat fibroblasts, HuH-7 human hepatocarcinoma cells, and SK-N-SH human neuroblastoma cells - were first examined with DNA microarrays. In all three cell lines, treatments with nobiletin (100 µM) for 24 h resulted in more than 200% increases in the expression levels of five genes, including the endoplasmic reticulum stress-responsive genes Ddit3, Trib3, and Asns, and in less than 50% decreases in the expression levels of seven genes, including the cell cycle-regulating genes Ccna2, Ccne2, and E2f8 and the oxidative stress-promoting gene Txnip. It was also confirmed that in each nobiletin-treated cell line, the levels of the DDIT3 (DNA-damage-inducible transcript 3, also known as CHOP and GADD153) and ASNS (asparagine synthetase) proteins were increased, while the level of the TXNIP (thioredoxin-interacting protein, also known as VDUP1 and TBP-2) protein was decreased. All these findings suggest that nobiletin exerts a wide variety of biological effects, at least partly, through induction of endoplasmic reticulum stress and suppressions of oxidative stress and cell proliferation.

Comparison of constitutive gene expression levels of hepatic cholesterol biosynthetic enzymes between Wistar-Kyoto and stroke-prone spontaneously hypertensive rats.

Serum total cholesterol amounts in the stroke-prone hypertensive rat (SHRSP) strain are lower than in the normotensive control strain, Wistar-Kyoto (WKY) rat. To understand the strain difference, constitutive gene expression levels of hepatic cholesterol biosynthetic enzymes in male 8-week-old SHRSP and WKY rats were comparatively examined by DNA microarray and real-time reverse transcription-polymerase chain reaction (RT-PCR) analyses. Of 22 cholesterol biosynthetic enzyme genes, expression levels of 8 genes, Pmvk, Idi1, Fdps, Fdft1, Sqle, Lss, Sc4mol, and Hsd17b7, in SHRSP were less than 50% those of the WKY rats; especially, the expression level of Sqle gene, encoding squalene epoxidase, a rate-limiting enzyme in cholesterol biosynthesis pathway, was about 20%. The gene expression level of sterol regulatory element-binding protein-2 (SREBP-2), which functions as a transcription factor upregulating gene expression of cholesterol biosynthetic enzymes, in SHRSP was about 70% of that in WKY rats. These results demonstrate the possibility that the lower serum total cholesterol level in SHRSP is defined by lower gene expression of most hepatic cholesterol biosynthetic enzymes. In particular, decreased gene expression level of Sqle gene might be the most essential factor. Moreover, the broad range of lowered rates of these genes in SHRSP suggests that the abnormal function and/or expression not only of SREBP-2 but also of one or more other transcription factors for those gene expressions exist in SHRSP.

Development of emotion comprehension in children with autism spectrum disorder and Williams syndrome.

Although research has shed light on the development of emotion comprehension in typically developing children, little is known about emotion comprehension in children who are developing atypically. Thus, this study examined the developmental trajectory of emotion understanding in non-clinical (NC) children and children with autism spectrum disorder (ASD) and Williams syndrome (WS) using a Test of Emotion Comprehension. In the test, we measured children's understanding of (I) recognition of emotions based on facial expressions, (II) external causes of emotions, (III) desire-based emotions, (IV) belief-based emotions, (V) the influence of a reminder on a present emotional state, (VI) regulating an experienced emotion, (VII) hiding an emotional state, (VIII) mixed emotions, and (IX) moral emotions. A Bayesian modeling approach was applied to compare the developmental trajectories of emotion understanding across the syndrome groups. The results revealed that NC children and children with WS followed significantly different developmental trajectories in specific aspects of emotion understanding, while children with ASD followed a very similar path to NC children. Children with ASD and NC children gradually developed an understanding of each component of emotion comprehension as they matured. However, the understanding of some components, such as desire-based emotions, hiding an emotional state, and moral emotions, in children with WS was affected by their Autism Spectrum Quotient scores. This is one of the first cross-syndrome studies to assess the development of emotion comprehension in children with ASD and WS, providing important insights for understanding the nature of disability and advancing the development of intervention programs.

Key factors for connecting silver-based icosahedral superatoms by vertex sharing.

Metal nanoclusters composed of noble elements such as gold (Au) or silver (Ag) are regarded as superatoms. In recent years, the understanding of the materials composed of superatoms, which are often called superatomic molecules, has gradually progressed for Au-based materials. However, there is still little information on Ag-based superatomic molecules. In the present study, we synthesise two di-superatomic molecules with Ag as the main constituent element and reveal the three essential conditions for the formation and isolation of a superatomic molecule comprising two Ag13-xMx structures (M = Ag or other metal; x = number of M) connected by vertex sharing. The effects of the central atom and the type of bridging halogen on the electronic structure of the resulting superatomic molecule are also clarified in detail. These findings are expected to provide clear design guidelines for the creation of superatomic molecules with various properties and functions.

Visual perspective-taking ability in 7- and 12-month-old infants.

Understanding how we see the world is different from how other people see it is a crucial part of social cognition and is known as visual perspective-taking. Although previous studies have demonstrated that 14-month-old infants have the capacity to compute the visual perspectives of others, it remains unknown whether infants under 12 months also have this ability. In this study, we modified a conventional gaze-following experimental setting in which one toy was placed in front of a model and was hidden by a barrier (Blocked Line of Sight Condition), and another toy was placed without a barrier (Clear Line of Sight Condition). We examined the visual perspective-taking abilities of 48 infants aged 7 and 12 months by measuring the infants' gaze shift towards the gaze-cued toy object with and without a barrier. The results demonstrated that 12-month-old infants could correctly follow a model's gaze if the model's line of sight was clear. In contrast, 7-month-old infants showed no evidence of such capacity. Our findings indicate that 12-month-old infants seem to have the capacity to compute the visual perspective of others.

Selective formation of [Au23(SPh t Bu)17]0, [Au26Pd(SPh t Bu)20]0 and [Au24Pt(SC2H4Ph)7(SPh t Bu)11]0 by controlling ligand-exchange reaction.

To use atomically precise metal nanoclusters (NCs) in various application fields, it is essential to establish size-selective synthesis methods for the metal NCs. Studies on thiolate (SR)-protected gold NCs (Au n (SR) m NCs) revealed that the atomically precise Au n (SR) m NC, which has a different chemical composition from the precursor, can be synthesized size-selectively by inducing transformation in the framework structure of the metal NCs by a ligand-exchange reaction. In this study, we selected the reaction of [Au25(SC2H4Ph)18]- (SC2H4Ph = 2-phenylethanethiolate) with 4-tert-butylbenzenethiol ( t BuPhSH) as a model ligand-exchange reaction and attempted to obtain new metal NCs by changing the amount of thiol, the central atom of the precursor NCs, or the reaction time from previous studies. The results demonstrated that [Au23(SPh t Bu)17]0, [Au26Pd(SPh t Bu)20]0 (Pd = palladium) and [Au24Pt(SC2H4Ph)7(SPh t Bu)11]0 (Pt = platinum) were successfully synthesized in a high proportion. To best of our knowledge, no report exists on the selective synthesis of these three metal NCs. The results of this study show that a larger variety of metal NCs could be synthesized size-selectively than at present if the ligand-exchange reaction is conducted while changing the reaction conditions and/or the central atoms of the precursor metal NCs from previous studies.

Comparison of the Social Responsiveness Scale-2 among Individuals with Autism Spectrum Disorder and Williams Syndrome in Japan.

This study examined the similarities/differences between the social phenotypes of Williams syndrome (WS) and autism spectrum disorder (ASD). As cultural norms may affect symptom evaluation, this study administered the Social Responsiveness Scale-2 to Japanese individuals with WS (n = 78, 4.4-44.0 years) and ASD (n = 75, 4.7-55.4 years). The scores for Social Motivation and Social Communication were significantly more severe in the ASD than WS group. Overall, the similarities and differences between the social phenotypes of the syndromes were consistent with the findings of a recent study conducted in the UK, except for the social awareness subscale score. This highlights the importance of cross-cultural investigations of WS and ASD.

Sensitivity to register selection errors amongst 5- and 7-year-old children.

We are expected to behave appropriately to suit social situations. One form of behavioral control is the selection of a linguistic register that is appropriate to the listener. Register selection errors can sometimes be interpreted as rude behavior and result in having a bad influence on the relationship with the listener and the evaluation by other people. Previous studies have demonstrated that children begin to show sensitivity to registers from about 2 years of age, and that 5- to 6-year-old children understand the appropriate relationships between a listener and a register. However, it remains unclear whether and when children understand the influence made by register selection errors on listeners, and how children evaluate speakers when they make errors in register selection. Therefore, we investigated the above issues in Japanese children, who are required to use registers strictly. Also, we conducted a control study with Japanese-speaking adults to identify adults' evaluation of register selection errors. The results indicated that 7-year-old, but not 5-year-old children understood that the selection of an appropriate register gives listeners positive feelings. Moreover, 7-year-old children used register selection as an index of selective learning and social preference, although how they use others' register use skills for evaluating them was slightly different from adults. These results suggest that although children notice the social meanings behind the use of registers by the age of 7, a more extended period of development is required to master the social meaning of register selection. (PsycINFO Database Record (c) 2019 APA, all rights reserved).

Sensitivity to linguistic register in 20-month-olds: Understanding the register-listener relationship and its abstract rules.

Linguistic register reflects changes in speech that depend on the situation, especially the status of listeners and listener-speaker relationships. Following the sociolinguistic rules of register is essential in establishing and maintaining social interactions. Recent research suggests that children over 3 years of age can understand appropriate register-listener relationships as well as the fact that people change register depending on their listeners. However, given previous findings that infants under 2 years of age have already formed both social and speech categories, it may be possible that even younger children can also understand appropriate register-listener relationships. The present study used Infant-Directed Speech (IDS) and formal Adult-Directed Speech (ADS) to examine whether 20-month-old toddlers can understand register-listener relationships. In Experiment 1, we used a violation-of-expectation method to examine whether 20-month-olds understand the individual associations between linguistic registers and listeners. Results showed that the toddlers looked significantly longer at a scene in which the adult was talked to in IDS than when the infant was talked to in IDS. In contrast, there was no difference when the adult and the infant were talked to in formal ADS. In Experiments 2 and 3, we used a habituation switch paradigm to examine whether 20-month-olds understand the abstract rule that a change of register depends on listeners rather than on speakers. Results showed that the toddlers looked significantly longer at the scene where the register rule was violated. The present findings provide new evidence that even 20-month-olds already understand that people change their way of speaking based on listeners, although their understanding of individual register-listener relationships is immature.

Children passively allow other's rule violations in cooperative situations.

Recent studies in developmental psychology have revealed the developmental origins of cooperation. Although such studies regard cooperation as a pro-social behavior, studies on adults have found a negative aspect: cooperation sometimes promotes unethical behavior. Adults also exhibit altruistic cheating, even though their cheating might not actually benefit them. However, the development of negative aspects of cooperation remains unclear. Our study examined whether 7-year-old children engage in negative aspects of cooperation from two aspects using a peeking paradigm. Specifically, Experiment 1 examined children's negative aspects of cooperation from the perspective of collaboration and Experiment 2 examined altruistic behavior. Results of Experiment 1 revealed that children kept the cheating of a collaborative partner secret even though they did not actively cheat themselves. In Experiment 2, children also kept the partner's cheating secret even when violations did not provide any reward to themselves, if the predefined reward was high. In contrast, children did not keep the cheating secret if the predefined reward was low. Overall, our findings suggest that even 7-year-olds tend to act as if cooperating is more important than following rules that are compatible and exhibit negative aspects of cooperation.

Measuring empathy for human and robot hand pain using electroencephalography.

This study provides the first physiological evidence of humans' ability to empathize with robot pain and highlights the difference in empathy for humans and robots. We performed electroencephalography in 15 healthy adults who observed either human- or robot-hand pictures in painful or non-painful situations such as a finger cut by a knife. We found that the descending phase of the P3 component was larger for the painful stimuli than the non-painful stimuli, regardless of whether the hand belonged to a human or robot. In contrast, the ascending phase of the P3 component at the frontal-central electrodes was increased by painful human stimuli but not painful robot stimuli, though the interaction of ANOVA was not significant, but marginal. These results suggest that we empathize with humanoid robots in late top-down processing similarly to human others. However, the beginning of the top-down process of empathy is weaker for robots than for humans.

Induced expression of hepatic N-methyl-D-aspartate receptor 2C subunit gene during liver enlargement induced by lead nitrate, a hepatocellular mitogen.

We previously demonstrated the super-induced expression of the Grin2c gene encoding the N-methyl-D-aspartate receptor 2C subunit during the development of liver enlargement with hepatocellular hypertrophy induced by phenobarbital, clofibrate, or piperonyl butoxide. In the present study, we assessed whether or not Grin2c gene expression was induced during the development of chemically induced liver enlargement with hyperplasia. Male Sprague-Dawley (SD) rats, stroke-prone spontaneously hypertensive rats (SHRSPs), and SHRSP's normotensive control, Wistar-Kyoto (WKY) rats, were administered lead nitrate (LN) (0.1 mmol/kg, single i.v.), a direct inducer of liver hyperplasia, and changes in the level of Grin2c mRNA in the liver were assessed by real-time RT-PCR. The level of hepatic Grin2c mRNA was significantly higher 6-48 hr after the injection in SD rats (about 30~40- and 70-fold over the control at 6~24 hr and 48 hr, respectively) and in WKY rats (about 20-fold over the control only at 12 hr), but was not significantly higher in SHRSPs. Such differences in LN-induced levels of Grin2c mRNA among SD rats, WKY rats, and SHRSPs were closely correlated with those in the previously reported increase in liver weight 48 hr after LN administration. The present findings suggest that the increase in the level of hepatic Grin2c mRNA relates to development of chemically induced liver enlargement with hyperplasia.

Change in the gene expression of the N-methyl-D-aspartate receptor 2C subunit by dietary ß-naphthoflavone, indole-3-carbinol, or acetaminophen in the rat liver.

We have previously demonstrated super-induced expression of the Grin2c gene encoding the N-methyl-D-aspartate receptor 2C subunit during the process of liver enlargement induced by phenobarbital, clofibrate, piperonyl butoxide, or lead nitrate. In the present study, hepatic Grin2c gene expression levels were assessed by real-time RT-PCR in male F344 rats fed for 3 days, 4 weeks, and 13 weeks a diet containing either ß-naphthoflavone (BNF) (5,000 ppm), indole-3-carbinol (I3C) (2,000 ppm), or acetaminophen (AA) (12,500 ppm until the first 14 days; 10,000 ppm from 15 days on), each of which is capable of inducing hepatocellular hypertrophy. Especially, either the 4-week or the 13-week treatment with each chemical, except for BNF, resulted in a drastic increase in the expression level of the Grin2c gene. DNA microarray analysis using RNAs of 13-week-treated rats showed that in the I3C- and AA-treated rats, the fold-increase rates of the Grin2c gene ranked second and first, respectively, among the genes analyzed. Histopathological analyses indicated that the slight hepatocellular hypertrophy in the periportal area and the hepatocellular necrosis in a portion of the centrilobular area developed in the BNF-treated and AA-treated rats, respectively. In addition, relative liver weight was significantly higher in the rats treated with BNF and I3C than in the control rats. The present findings suggest the possibility that the induction of Grin2c gene expression is not necessarily dependent on only the development of liver enlargement, although the significance of this induction remains unclear.