Sulfur-Tuned Main-Group Sb-N-C Catalysts for Selective 2-Electron and 4-Electron Oxygen Reduction.

The selective oxygen reduction reaction (ORR) is important for various energy conversion processes such as the fuel cells and metal-air batteries for the 4e- pathway and hydrogen peroxide (H2O2) electrosynthesis for the 2e- pathway. However, it remains a challenge to tune the ORR selectivity of a catalyst in a controllable manner. Herein, an efficient strategy for introducing sulfur dopants to regulate the ORR selectivity of main-group Sb-N-C single-atom catalysts  is reported. Significantly, Sb-N-C with the highest sulfur content follows a 2e- pathway with high H2O2 selectivity (96.8%) and remarkable mass activity (96.1 A g-1 at 0.65 V), while the sister catalyst with the lowest sulfur content directs a 4e- pathway with a half-wave potential (E1/2 = 0.89 V) that is more positive than commercial Pt/C. In addition, practical applications for these two 2e-/4e- ORR catalysts are demonstrated by bulk H2O2 electrosynthesis for the degradation of organic pollutants and a high-power zinc-air battery, respectively. Combined experimental and theoretical studies reveal that the excellent selectivity for the sulfurized Sb-N-Cs is attributed to the optimal adsorption-desorption of the ORR intermediates realized through the electronic structure modulation by the sulfur dopants.

Working memory components modulation of attentional disengagement from evaluative distractor.

It is important for people to disengage attention from a distraction, which can help them complete the task at hand as quickly as possible. Recent studies have shown that people's attention stays longer on reward-distractors than on loss-distractors, and a delay in attentional disengagement is noted when reward-distractors are present. However, few studies have examined whether attentional disengagement from an evaluative distractor relies upon working memory (WM) components. In the present study, we used an attentional disengagement paradigm in which reward- or loss-distractors were presented at a central location and the target was presented at a peripheral location, in combination with different WM tasks. The results from Experiment 1 showed that participants were slower to disengage their attention from a central reward-distractor than a loss-distractor regardless of cognitive load when the phonological loop component of WM was involved. The results from Experiment 2 revealed that people had difficulty in shifting their attention away from a reward-distractor in comparison to a loss-distractor when spatial WM was low, whereas no such difference was observed when spatial WM was high. We conclude that WM components differently modulate attentional disengagement from evaluative distractors. That is, the processing of evaluative (reward and loss) distractors may rely on the same cognitive resources as the spatial WM component, but not the phonological loop component.

Ketocyanine-Based Fluorescent Probe Revealing the Polarity Heterogeneity of Lipid Droplets and Enabling Accurate Diagnosis of Hepatocellular Carcinoma.

Hepatocellular carcinoma (HCC) has gradually become a pronoun for terrifying death owing to its high mortality rate. With the progression of HCC, lipid droplets (LDs) in HCC cells exhibit specific variations such as increased LDs number and decreased polarity, which can serve as the diagnostic target. However, developing an effective method to achieve HCC diagnosis and reveal LDs polarity heterogeneity is still a crucial challenge. Herein, the first high-performance LDs-targeting probe (1) is reported based on ketocyanine strategy with ultrasensitive polarity-responding ability and near-infrared emission. Probe 1 shows excellent sensitivity to polarity parameter Δf (0.027-0.290) with 808-fold fluorescence enhancement and the emission wavelength red-shifts 91 nm. In HCC cells, probe 1 shows a 2.5- to 5.9-fold fluorescence enhancement compared with normal and other cancer cells which exceeds clinical threshold of 2.0, indicating probe 1 can distinguish HCC cells. The LDs polarity heterogeneity is revealed and it displays a sequence, HCC cells < other cancer cells < normal cells, which may provide useful insight to engineer LDs-targeting probes for HCC cell discrimination. Finally, probe 1 realizes accurate HCC diagnosis on the cellular, organ, and in vivo levels, providing a satisfying tool for clinical HCC diagnosis and surgical navigation.

Highly Durable and Efficient Seawater Electrolysis Enabled by Defective Graphene-Confined Nanoreactor.

Direct seawater electrolysis is a promising technology for massive green hydrogen production but is limited by the lack of durable and efficient electrocatalysts toward the oxygen evolution reaction (OER). Herein, we develop a core-shell nanoreactor as a high-performance OER catalyst consisting of NiFe alloys encapsulated within defective graphene layers (NiFe@DG) by a facile microwave shocking strategy. This catalyst needs overpotentials of merely 218 and 276 mV in alkalized seawater to deliver current densities of 10 and 100 mA cm-2, respectively, and operates continuously for 2000 h with negligible activity decay (1.0%), making it one of the best OER catalysts reported to date. Detailed experimental and theoretical analyses reveal that the excellent durability of NiFe@DG originates from the formation of the built-in electric field triggered by the defective graphene coating against chloride ions at the electrode/electrolyte interface, thus protecting the active NiFe alloys at the core from dissolution and aggregation under harsh operation conditions. Further, a highly stable and efficient seawater electrolyzer is assembled with the NiFe@DG anode and the Pt/C cathode to demonstrate the practicability of the catalysts.

Rewarding outcomes enhance attentional capture and delay attentional disengagement.

Attentional capture and disengagement are distinct process involved in attentional orienting. Most current studies have examined either the process of attentional capture or disengagement by manipulating stimuli associated with either positive (gains) or negative outcomes (losses). However, few studies have investigated whether attentional capture and disengagement are modulated by reward and loss outcomes. In the current study, we want to examine whether positive or negative outcomes could modulate distinguishing process of attentional capture and disengagement. Here, we manipulated different colored singleton stimuli associated with reward or loss outcomes; these stimuli were either presented at the center of screen or at the peripheral location. The participants' task was to search the target and identify the orientation of line segment in target as quickly as possible. The results showed that people had difficulty disengaging from a central reward-distractor, in comparison to loss- and neutral-distractor when target was presented at peripheral location. Similarly, peripheral reward-distractor captured more attention than loss- and neutral-distractor when target was presented at the center of screen after central fixation disappeared. Through our discoveries, we can conclude that positive rewards can increase attentional capture and delay attentional disengagement in healthy people.

Sb2S3-templated synthesis of sulfur-doped Sb-N-C with hierarchical architecture and high metal loading for H2O2 electrosynthesis.

Selective two-electron (2e-) oxygen reduction reaction (ORR) offers great opportunities for hydrogen peroxide (H2O2) electrosynthesis and its widespread employment depends on identifying cost-effective catalysts with high activity and selectivity. Main-group metal and nitrogen coordinated carbons (M-N-Cs) are promising but remain largely underexplored due to the low metal-atom density and the lack of understanding in the structure-property correlation. Here, we report using a nanoarchitectured Sb2S3 template to synthesize high-density (10.32 wt%) antimony (Sb) single atoms on nitrogen- and sulfur-codoped carbon nanofibers (Sb-NSCF), which exhibits both high selectivity (97.2%) and mass activity (114.9 A g-1 at 0.65 V) toward the 2e- ORR in alkaline electrolyte. Further, when evaluated with a practical flow cell, Sb-NSCF shows a high production rate of 7.46 mol gcatalyst-1 h-1 with negligible loss in activity and selectivity in a 75-h continuous electrolysis. Density functional theory calculations demonstrate that the coordination configuration and the S dopants synergistically contribute to the enhanced 2e- ORR activity and selectivity of the Sb-N4 moieties.

Red-emitting carbon dots aggregates-based fluorescent probe for monitoring Cu2.

R-CDAs have been synthesized in a one-pot solvothermal procedure starting from 3,4-diaminobenzoic acid in an acidic medium. Transmission electron microscopy (TEM) revealed that R-CDAs nanoparticles exhibited a much larger diameter of 7.2-28.8 nm than traditional monodisperse carbon dots. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR) revealed the presence of polar functional groups (hydroxyl, amino, carboxyl) on the surface of R-CDAs. Upon excitation with visible light (550 nm), R-CDAs emit stable, red fluorescence with a maximum at 610 nm. Under the optimum conditions, Cu2+ ions quench the fluorescence of this probe, and the signal is linear in a concentration range of copper ions between 5 and 600 nM with the detection limit of only 0.4 nM. Recoveries from 98.0 to 105.0% and relative standard deviations (RSD) from 2.8 to 4.5% have been obtained for detection of Cu2+ in real water samples. Furthermore, the R-CDAs fluorescent probe showed negligible cytotoxicity toward HeLa cells and good bioimaging ability, suggesting its potential applicability as a diagnostic tool in biomedicine.

Stress-induced impairment reveals the stage and features of post-error adaptive adjustment.

An increased reaction time often occurs after error responses (post-error slowing, PES). However, the role of top-down regulation in post-error processing remains to be debated. Impairing cognitive control function through acute stress would help to investigate the role and stage of top-down adaptive regulation in post-error processing. Here, we recruited 50 healthy male participants who were randomly assigned to either a stress condition (Trier Social Stress Task, TSST) or a control condition (control version of the TSST). A color-word Stroop task with different response stimulus intervals (RSIs) was used to investigate the effects of acute stress on different stages of post-error processing. The results showed that cortisol, heart rate, perceived stress level, and negative affect were higher in the stress group (n = 24) than in the control group (n = 26), indicating successful stress induction. The accuracy of post-error response in the control group increased with the extension of RSI, and the reaction time decreased. However, the accuracy of 1,200 ms RSI was close to that of 700 ms RSI in the stress group but was significantly lower than that in the control group. The results suggested that acute stress caused the impairment of top-down adaptive regulation after error. Furthermore, our study manifested adaptive adjustment only in the late stages of post-error processing, indicating the phasic and adaptive features of post-error adjustment.

Evaluative distractors modulate attentional disengagement: People would rather stay longer on rewards.

Attentional disengagement is of great significance to individuals adapting to their environment who can benefit from disregarding the attraction of salient and task-irrelevant objects. Previous studies have suggested that, in addition to causing greater financial loss compared with neutral distractors, reward distractors hold attention longer than neutral distractors. However, few studies have directly compared the attentional disengagement differences between reward-associated and loss- or punishment-associated stimuli. In the current study, we used different color singleton stimuli tied to reward or punishment outcomes; the stimuli were present in the center of the screen. Participants were required to respond to a line within the target at a peripheral location. The results showed that the response to the target was slower when the central distractor was associated with a reward than with punishment. This finding reflects that, although participants understand that reward-associated and punishment-associated stimuli have an equal opportunity for the same economic benefit, they still take longer to disengage from a reward distractor compared with a punishment distractor.

Engineering the Morphology and Microenvironment of a Graphene-Supported Co-N-C Single-Atom Electrocatalyst for Enhanced Hydrogen Evolution.

Graphene-supported single-atom catalysts (SACs) are promising alternatives to precious metals for catalyzing the technologically important hydrogen evolution reaction (HER), but their performances are limited by the low intrinsic activity and insufficient mass transport. Herein, a highly HER-active graphene-supported Co-N-C SAC is reported with unique design features in the morphology of the substrate and the microenvironment of the single metal sites: i) the crumpled and scrolled morphology of the graphene substrate circumvents the issues encountered by stacked nanoplatelets, resulting in improved exposure of the electrode/electrolyte interfaces (≈10 times enhancement); ii) the in-plane holes in graphene preferentially orientate the Co atoms at the edge sites with low-coordinated Co-N3 configuration that exhibits enhanced intrinsic activity (≈2.6 times enhancement compared to the conventional Co-N4 moiety), as evidenced by detailed experiments and density functional theory calculations. As a result, this catalyst exhibits significantly improved HER activity with an overpotential (η) of merely 82 mV at 10 mA cm-2 , a small Tafel slope of 59.0 mV dec-1 and a turnover frequency of 0.81 s-1 at η = 100 mV, ranking it among the best Co-N-C SACs.

Electronic Structure Regulation of Single-Atom Catalysts for Electrochemical Oxygen Reduction to H2 O2.

Electrochemical synthesis of hydrogen peroxide (H2 O2 ) via the 2-electron oxygen reduction reaction (ORR) has emerged as a promising alternative to the energy-intensive anthraquinone process and catalysts combining high selectivity with superior activity are crucial for enhancing the efficiency of H2 O2 electrosynthesis. In recent years, single-atom catalysts (SACs) with the merits of maximum atom utilization efficiency, tunable electronic structure, and high mass activity have attracted extensive attention for the selective reduction of O2 to H2 O2 . Although considerable improvements are made in the performance of SACs toward the 2-electron ORR process, the principles for modulating the catalytic properties of SACs by adjusting the electronic structure remain elusive. In this review, the regulation strategies for optimizing the 2-electron ORR activity and selectivity of SACs by different methods of electronic structure tuning, including the altering of the central metal atoms, the modulation of the coordinated atoms, the substrate effect, and alloy engineering are summarized. Finally, the challenges and future prospects of advanced SACs for H2 O2 electrosynthesis via the 2-electron ORR process are proposed.

Iodine-Doping-Induced Electronic Structure Tuning of Atomic Cobalt for Enhanced Hydrogen Evolution Electrocatalysis.

The development of strategies for tuning the electronic structure of the metal sites in single-atom catalysts (SACs) is the key to optimizing their activity. Herein, we report that iodine doping within the carbon matrix of a cobalt-nitrogen-carbon (Co-N-C) catalyst can effectively modulate its electronic structure and catalytic activity toward the hydrogen evolution reaction (HER). The iodine-doped Co-N-C catalyst shows exceptional HER activity in acid with an overpotential of merely 52 mV at 10 mA cm-2, a small Tafel slope of 56.1 mV dec-1, making it among the best SACs based on both precious and nonprecious metals. Moreover, this catalyst possesses a high turnover frequency (TOF) value of 1.88 s-1 (η = 100 mV), which is about 1 order of magnitude larger than that (0.2 s-1) of the iodine-free counterpart. Experimental and theoretical studies demonstrate that the introduction of iodine dopants lowers the chemical oxidation state of the Co sites, resulting in the optimized hydrogen adsorption and facilitated HER kinetics. This work provides an alternative strategy to regulate the electronic structure of SACs for improved performance.

Quantitative Structure-Activity Relationship Enables the Rational Design of Lipid Droplet-Targeting Carbon Dots for Visualizing Bisphenol A-Induced Nonalcoholic Fatty Liver Disease-like Changes.

Lipid droplets (LDs) play indispensable roles in numerous physiological processes; hence, the visualization of the dynamic behavior of LDs in living cells is of great importance in physiological and pathological research. In this article, the quantitative structure-activity relationship (QSAR) theory was employed as an effective design strategy for the development of organelle-targeting carbon dots (CDs). The lipid-water partition coefficient (Log P) of the QSAR was adopted as a key parameter to predict the cellular uptake and subcellular localization of CDs in live cells. By carefully adjusting the molecular structure and lipophilicity of the precursors, p-phenylenediamine-derivatized nucleolus-targeting hydrophilic CDs were converted to lipophilic CDs [4-piperidinoaniline (PA) CDs] with inherent LD-targeting performance. The PA CDs were able to indicate the dynamic behavior of LDs and visualize the changes of bisphenol A-induced nonalcoholic fatty liver disease-like changes in a cellular model. The QSAR strategy of CDs demonstrated here is expected to be increasingly exploited as a powerful design tool for developing various organelle-targeting CDs.

Design of Aligned Porous Carbon Films with Single-Atom Co-N-C Sites for High-Current-Density Hydrogen Generation.

Metal- and nitrogen-doped carbon (M-N-C) materials as a unique class of single-atom catalysts (SACs) have increasingly attracted attention as the replacement of platinum for the hydrogen evolution reaction (HER); however, their employment as HER electrodes at high current densities of industrial level remains a grand challenge. Herein, an aligned porous carbon film embedded with single-atom Co-N-C sites of exceptional activity and stability at high current densities is designed. Within the film, the atomic CoNx moieties exhibit high intrinsic activity, while the multiscale porosity of the carbon frameworks with vertically aligned microchannels afford facilitated mass transfer under the conditions of high production rate and ultrathick electrodes. Moreover, the superwetting properties of the film promote electrolyte wetting and ensure the timely removal of the evolving H2 gas bubbles. The as-designed film can work as an efficient HER electrode to deliver 500 and 1000 mA cm-2 in acid at overpotentials of 272 and 343 mV, respectively, and can operate uninterruptedly and stably at 1000 mA cm-2 for at least 32 h under static conditions. These findings pave the road toward the rational design of SACs with improved activity and stability at high current densities in gas-evolving electrocatalytic processes.

'Turn-on' fluorescence sensing of hydrogen peroxide in marine food samples using a carbon dots-MnO2 probe.

A 'turn-on' fluorescence method for detection of hydrogen peroxide (H2 O2 ) in marine food samples is presented in this article. Using this method, a carbon dots (CDs)-MnO2 probe was formed in which fluorescence intensity (FI) of CDs was quenched through fluorescence resonance energy transfer by addition of MnO2 nanosheets. When H2 O2 was added into the CDs-MnO2 solution, the MnO2 nanosheets formed Mn2+ ions due to a redox reaction between H2 O2 and MnO2 nanosheets, and CD FI was recovered. Under optimized conditions, the detection limit for H2 O2 was 0.87 µM, and analytical linear range was 4-100 µM. Furthermore, this developed fluorescence sensing system was successfully used with satisfactory results to determine trace H2 O2 content in marine food samples.

Effects of mixotrophic cultivation on antioxidation and lipid accumulation of Chlorella vulgaris in wastewater treatment.

The effects of mixotrophic cultivation on antioxidation and lipid production of Chlorella vulgaris in wastewater treatment were analyzed. The biomass and lipid content of the mixotrophic C. vulgaris cultured in wastewater were higher compared with the autotrophic C. vulgaris cultured in BG-11. The mixotrophic C. vulgaris provided more fatty acids as the contents of total fatty acids rose. The unsaturated fatty acid/total fatty acid ratio under mixotrophic cultivation was up to 0.91, indicating the mixotrophic cultivation system was applicable for the generation of unsaturated fatty acids. Activities of antioxidant enzymes such as superoxide dismutase and glutathione peroxidase were improved after the addition of wastewater to algal cultures. Moreover, the activity and starch formation of ADP-glucose pyrophosphorylase decreased and the activity of acetyl-CoA carboxylase was enhanced, which contributed to the lipid production in the mixotrophic C. vulgaris in wastewater. This study suggests mixotrophic cultivation of microalgae in wastewater is an efficient way to improve lipid production.

Graphene Nanoarchitectonics: Recent Advances in Graphene-Based Electrocatalysts for Hydrogen Evolution Reaction.

Under the double pressures of both the energy crisis and environmental pollution, the exploitation and utilization of hydrogen, a clean and renewable power resource, has become an important trend in the development of sustainable energy-production and energy-consumption systems. In this regard, the electrocatalytic hydrogen evolution reaction (HER) provides an efficient and clean pathway for the mass production of hydrogen fuel and has motivated the design and construction of highly active HER electrocatalysts of an acceptable cost. In particular, graphene-based electrocatalysts commonly exhibit an enhanced HER performance owing to their distinctive structural merits, including a large surface area, high electrical conductivity, and good chemical stability. Considering the rapidly growing research enthusiasm for this topic over the last several years, herein, a panoramic review of recent advances in graphene-based electrocatalysts is presented, covering various advanced synthetic strategies, microstructural characterizations, and the applications of such materials in HER electrocatalysis. Lastly, future perspectives on the challenges and opportunities awaiting this emerging field are proposed and discussed.

Social Company Disrupts Fear Memory Renewal: Evidence From Two Rodent Studies.

Renewal of fear outside treatment context is a challenge for behavioral therapies. Prior studies suggest a social buffering effect that fear response is attenuated in the presence of social company. However, few studies have examined the role of social company in reducing fear renewal. Here, we used a Pavlovian fear conditioning procedure including acquisition, extinction and test stages to examine social buffering effect on fear memory renewal in male rats. The test context was manipulated to be either different from the extinction one in ABC model, or same as that in ACC model. All conditioned subjects underwent extinction individually in Experiment 1 but with a partner in Experiment 2. In test, both experiments manipulated social company (alone vs. accompanied) and context (ABC vs. ACC). Experiment 1 showed more freezing in ABC than in ACC model during the test-alone condition, indicating a fear renewal effect which, however, was absent during the test-accompanied condition. Also, accompanied subjects showed less freezing compared to alone subjects in the ABC model. In Experiment 2, animals showed a similar freezing in ABC and ACC models despite being tested alone, implying that social company offered at extinction disrupted fear renewal. Again, we observed reduced freezing in accompanied relative to alone subjects in the test. These results suggest that social company is effective in disrupting fear renewal after leaving treatment context.

Repeated administration of 5-hydroxytryptamine 2C agonist MK212 produces a sensitization effect of antipsychotic activity.

5-Hydroxytryptamine 2C (5-HT2C ) receptor agonists have been suggested to possess an antipsychotic activity in several acute preclinical tests of antipsychotic drugs with low extra-pyramidal side effect liability. However, little is known about the long-term effect associated with chronic use of 5-HT2C receptor agonists. The present study examined whether repeated activation of 5-HT2C receptor with a highly selective 5-HT2C receptor agonist MK212 would induce a long-term change in its antipsychotic-like activity (either a sensitization or tolerance) in the conditioned avoidance response and MK801-induced hyperlocomotion tests. Sprague-Dawley rats were first tested under the intraperitoneal (i.p.) treatment of MK212 (0.25, 0.5, 1.0 mg/kg) for 5 consecutive days. Three days later, when all rats were injected with a low dose of MK 212 (0.25 mg/kg) and tested for avoidance responding, rats that had been pretreated with 1.0 and 0.5 mg/kg MK212 made significantly fewer avoidance responses than those that had been treated with vehicle (0.9% saline). However, this past drug exposure-induced group difference was not significant in the MK801-induced hyperlocomotion test. Overall, results from this study suggest that repeated treatment of MK212 is capable of inducing a dose-dependent sensitization of antipsychotic activity in conditioned avoidance response. The discrepancy in sensitization of MK212 in CAR and MK801-induce hyperlocomotion may be related to the different mechanism underlying the effect of MK212 in these two tests. © 2016 IUBMB Life, 68(12):985-993, 2016.

Effects of 7-nitroindazole, a selective neural nitric oxide synthase inhibitor, on context-shock associative learning in a two-process contextual fear conditioning paradigm.

Nitric oxide (NO) is an important retrograde neuronal intracellular messenger which plays an important role in synaptic plasticity and is involved in learning and memory. However, evidence that NO is particularly important for the acquisition of contextual fear conditioning is mixed. Also, little is known about at which stages of the contextual fear conditioning does NO make its contribution. In the present study, we used 7-nitroindazole to temporarily inhibit neural nitric oxide synthase at either the pre-exposure stage or conditioning stage in a two-process paradigm and examined the potential contribution that NO makes to the contextually conditioned fear. Results showed that the expression of contextual fear memory was significantly impaired in rats treated with 7-nitroindazole (30mg/kg, i.p.) prior to the pairing of context-shock (p=0.034, n=8), but not after the conditioning phase (p=0.846, n=8). In addition, the expression of contextual fear memory and reconsolidation was not significantly impaired by 7-nitroindazole administered prior to the context pre-exposure stage or prior to another context-shock learning. These findings suggest that NO is specifically involved in the acquisition but not the consolidation, retrieval or reconsolidation of contextual fear memory.