The perceived controllability of negatively-valenced episodic future thinking modulates delay discounting.

Intertemporal decision-making is important for both economy and physical health. Nevertheless, in daily life, individuals tend to prefer immediate and smaller rewards to delayed and larger rewards, which is known as delay discounting (DD). Episodic future thinking (EFT) has been proven to influence DD. However, there is still no inconsistent conclusion on the effect of negative EFT on DD. Considering the perceived controllability of negative EFT may address the issue (Controllability refers to the extent to which progress and result of an event could be controlled by ourselves). In the current study, we manipulated EFT conditions (baseline, neutral EFT, negative-controllable EFT and negative-uncontrollable EFT), delayed time (i.e. 1 week, 1 month, 3 months, 6 months, 1 year and 3 years) and reward magnitude (small, large). We mainly found that when experiencing negative-uncontrollable EFT compared to negative-controllable EFT in the delayed time of 6 months with large rewards, individuals chose more delayed rewards, suggesting that negative-uncontrollable EFT effectively reduced DD under conditions of both large-magnitude reward and longer delayed time. The current study provides new insight for healthy groups on optimising EFT. In that case, individuals are able to gain long-term benefits in financial management and healthcare.

Cognitive reappraisal and affective response to physical activity: associations with physical activity behavior.

OBJECTIVE: Cognitive reappraisal (CR), as an adaptive emotion regulation strategy, may play a role in transforming affect in a positive direction during or after exercise, thereby supporting physical activity (PA) adherence. The present study aimed to test the associations among PA, CR frequency, and affective response to PA, and further to examine the role of CR on PA behavior through affective response. METHODS: A cross-sectional study was conducted with a sample of 105 adults, 74 of whom were women, with a mean age of 25.91. Self-report scales were used to measure PA, CR, and affective response to PA. Along with scales, demographic questions on age, sex, and education level were included. Data was collected via an online questionnaire. RESULTS: The frequency of CR use was positively associated with affective response, and affective response with PA behavior. Mediation analysis revealed that affective response mediated the relationship between CR and PA. DISCUSSION: Results were in the expected direction demonstrating the mediating role of affective response between CR and PA which implies that PA adherence might be facilitated by CR engagement. PA intervention programs should consider implementing CR ability and use frequency improving techniques.

Sub-Nanosheet Induced Inverse Growth of Negative Valency Au Clusters for Tumor Treatment by Enhanced Oxidative Stress.

Cluster aggregation states are thermodynamically favored at the subnanoscale, for which an inverse growth from nanoparticles to clusters may be realized on subnanometer supports. Herein, we develop Au-polyoxometalate-layered double hydroxide (Au-POM-LDH) sub-1 nm nanosheets (Sub-APL) based on the above strategy, where sub-1 nm Au clusters with negative valence are generated by the in-situ disintegration of Au nanoparticles on POM-LDH supports. Sub-1 nm Au clusters with ultrahigh surface atom ratios exhibit remarkable efficiency for glutathione (GSH) depletion. The closely connected sub-1 nm Au with negative valence and POM hetero-units can promote the separation of hole-electrons, resulting in the enhanced reactive oxygen species (ROS) generation under ultrasound (US). Besides, the reversible redox of Mo in POM is able to deplete GSH and trigger chemodynamic therapy (CDT) simultaneously, further enhancing the oxidative stress. Consequently, the Sub-APL present 2-fold ROS generation under US and 7-fold GSH depletion compared to the discrete Au and POM-LDH mixture. Therefore, the serious imbalance of redox in the TME caused by the sharp increase of ROS and rapid decrease of GSH leads to death of tumor ultimately.

Bidirectional valence coding in amygdala intercalated clusters: A neural substrate for the opponent-process theory of motivation.

Processing emotionally meaningful stimuli and eliciting appropriate valence-specific behavior in response is a critical brain function for survival. Thus, how positive and negative valence are represented in neural circuits and how corresponding neural substrates interact to cooperatively select appropriate behavioral output are fundamental questions. In previous work, we identified that two amygdala intercalated clusters show opposite response selectivity to fear- and anxiety-inducing stimuli - negative valence (Hagihara et al., 2021). Here, we further show that the two clusters also exhibit distinctly different representations of stimuli with positive valence, demonstrating a broader role of the amygdala intercalated system beyond fear and anxiety. Together with the mutually inhibitory connectivity between the two clusters, our findings suggest that they serve as an ideal neural substrate for the integrated processing of valence for the selection of behavioral output.

Towards enhanced performance: an integrated framework of emotional valence, arousal, and task demand.

Extensive evaluations exist concerning the linkage between objective task demands and subsequent effects on user performance. However, the human user also experiences a range of emotions related to external task demands. Problematically, little is known about the associations between emotional valence, and arousal associated with the task demand-performance axis. In this paper, we advance a theoretical model concerning such interactive influences using three dimensions: (1) emotional valence, (2) arousal, and (3) task demand. The model evaluates the impact of these dimensions on user performance. It also identifies critical emotional user states, particularly those resulting in negative performance effects, as well as non-critical emotional states that can positively impact performance. Finally, we discuss the implications for affect-adaptive systems that can mitigate the impact of critical emotional states while leveraging the benefits of non-critical ones.

To effectively model performance and prevent errors in safety-critical human-machine systems, it is crucial to consider user states of emotional valence, arousal, and the current task demand. The proposed model enables the classification of critical and non-critical states within affect-adaptive systems. States characterised by negative valence, high arousal, and overload should be avoided to foster high performance, especially in safety-critical environments. Additionally, the present work offers recommendations for preserving and restoring non-critical states to ensure optimal performance and provides implications for training.

Fabrication of 3D CuFe2O4/Cu0 hierarchical nanostructures on carbon fiber paper by simple hydrothermal method for efficient detection of malachite green, sunset yellow and tartrazine in food samples.

In this study, a hydrothermal process was utilized to grow mixed-valence CuFe2O4/Cu0 nanosheets on carbon fiber paper, forming a three-dimensional hierarchical electrode (CuFe2O4/Cu0@CFP). The ordered array structure, coupled with the porous bowl-like structure, enhances the exposure of more electrode active sites and facilitates analyte penetration, thus enhancing the electrode sensing performance. As a binder-free sensor, the CuFe2O4/Cu0@CFP sensor exhibited remarkable sensitivity in detecting Malachite Green (MG), Sunset Yellow (SY) and Tartrazine (TA) over wide concentration ranges: 0.1-300 µM for MG (R2 = 0.994), 0.005-200 µM for SY (R2 = 0.996), and 0.005-300 µM for TA (R2 = 0.995) with low detection limits of 0.033 µM for MG, 0.0016 µM for SY, and 0.0016 µM for TA (S/N = 3), respectively. Additionally, the 3D CuFe2O4/Cu0@CFP sensor detected MG, SY, and TA in a mixed solution with satisfactory results. It also performs well in beverage, fruit juice powder, and jelly samples, with results matching those from HPLC.

Blunted midbrain reward activation during smoking withdrawal: a preliminary study.

Introduction: Tobacco smoking is the leading preventable cause of death, causing more than six million deaths annually worldwide, mainly due to cardiovascular disease and cancer. Many habitual smokers try to stop smoking but only about 7% are successful, despite widespread knowledge of the risks. Development of addiction to a range of substances is associated with progressive blunting of brain reward responses and sensitisation of stress responses, as described by the allostasis theory of addiction. There is pre-clinical evidence from rodents for a dramatic decrease in brain reward function during nicotine withdrawal. Methods: Here we tested the hypothesis that habitual smokers would also exhibit blunted reward function during nicotine withdrawal using a decision-making task and fMRI. Results: Our findings supported this hypothesis, with midbrain reward-related responses particularly blunted. We also tested the hypothesis that smokers with a longer duration of smoking would have more pronounced abnormalities. Contrary to expectations, we found that a shorter duration of smoking in younger smokers was associated with the most marked abnormalities, with blunted midbrain reward related activation including the dopaminergic ventral tegmental area. Discussion: Given the substantial mortality associated with smoking, and the small percent of people who manage to achieve sustained abstinence, further translational studies on nicotine addiction mechanisms are indicated.

Differential functions of the dorsal and intermediate regions of the hippocampus for optimal goal-directed navigation in VR space.

Goal-directed navigation requires the hippocampus to process spatial information in a value-dependent manner, but its underlying mechanism needs to be better understood. Here, we investigated whether the dorsal (dHP) and intermediate (iHP) regions of the hippocampus differentially function in processing place and its associated value information. Rats were trained in a place-preference task involving reward zones with different values in a visually rich virtual reality environment where two-dimensional navigation was possible. Rats learned to use distal visual scenes effectively to navigate to the reward zone associated with a higher reward. Inactivation of both dHP and iHP with muscimol altered the efficiency and precision of wayfinding behavior, but iHP inactivation induced more severe damage, including impaired place preference. Our findings suggest that the iHP is more critical for value-dependent navigation toward higher-value goal locations.

The neural structures of theory of mind are valence-sensitive: evidence from three tDCS studies.

Several cortical structures are involved in theory of mind (ToM), including the dorsolateral prefrontal cortex (dlPFC), the ventromedial prefrontal cortex (vmPFC), and the right temporo- parietal junction (rTPJ). We investigated the role of these regions in mind reading with respect to the valence of mental states. Sixty-five healthy adult participants were recruited and received transcranial direct current stimulation (tDCS) (1.5 mA, 20 min) with one week interval in three separate studies. The stimulation conditions were anodal tDCS over the dlPFC coupled with cathodal tDCS over the vmPFC, reversed stimulation conditions, and sham in the first study, and anodal tDCS over the vmPFC, or dlPFC, and sham stimulation, with an extracranial return electrode in the second and third study. During stimulation, participants underwent the reading mind from eyes/voice tests (RMET or RMVT) in each stimulation condition. Anodal left dlPFC/cathodal right vmPFC stimulation increased the accuracy of negative mental state attributions, anodal rTPJ decreased the accuracy of negative and neutral mental state attributions, and decreased the reaction time of positive mental state attributions. Our results imply that the neural correlates of ToM are valence-sensitive.

Solvent Effect on Dative and Ionic Bond Strengths: A Unified Theory from the Potential Analysis and Valence Bond (VB) Computation.

Solvent molecules interact with a solute through various intermolecular forces. Here we employed a potential energy surface (PES) analysis to interpret the solvent-induced variations in the strengths of dative (Me3NBH3) and ionic (LiCl) bonds, which possess both ionic and covalent (neutral) characteristics. The change of a bond is driven by the gradient (force) of the solvent-solute interaction energy with respect to the focused bond length. Positive force shortens the bond length and increases the bond force constant, leading to a blue-shift of the bond stretching vibrational frequency upon solvation. Conversely, negative force elongates the bond, resulting in a reduced bond force constant and red-shift of the stretching vibrational frequency. The different responses of Me3NBH3 and LiCl to solvation are studied with valence bond (VB) theory, as Me3NBH3 and LiCl are dominated by the neutral covalent VB structure and the ionic VB structure, respectively. The dipole moment of an ionic VB structure increases along the increasing bond distance, while the dipole moment of a neutral covalent VB structure increases with the decreasing bond distance. The roles of the dominating VB structures are further examined by the geometry optimizations and frequency calculations with the block-localized wavefunction (BLW) method.

Fe/Cu MOFs of Fe2+-rich and Cu-doping via in situ reduction as nanozyme for peroxidase-like catalycity enhancement.

Fe-MOFs of mixed valence was synthesized by a solvothermal method via the in-situ reduction of ethylene glycol (EG) pre-coordination with the proper ratio of Fe2+/Fe3+ between 0.83 and 2.46. Synchronously with copper introduction, the Fe/Cu MOFs of mixed valence (Fe/Cu-MVMOFs) was then one pot acquired to remarkably improve the affinity of Fe2+ and Cu+ to H2O2 and promote the conversion efficiency of Fe2+/Fe3+ via the electron transfer among Fe-Cu bimetal clusters (XPS and XRD). Hence, the maximum reaction rate of H2O2 with Fe/Cu-MVMOFs reached 16.65 M·s-1, along with Km as low as 0.0479 mM. H2O2 and glutathione (GSH) were efficiently detected, ranging from 0.25 to 60 µM and from 0.2 to 40 µM, respectively. The investigation of catalyzation selectivity and practical serum detection by Fe/Cu-MVMOFs illustrated the efficacy and efficiency, denoting Fe/Cu-MVMOFs as the promising peroxidase candidate.

Exploiting Mixed Valence Charge Transfer for Electrochromic and Electrofluorochromic Use.

An asymmetric mixed valence fluorophore with two different electron rich termini was investigated as a dual-role active material for electrochromism and electrofluorochromism. The fluorescence quantum yield (Φfl) and emission wavelength of the fluorophore were dependent on solvent polarity. The quantum yield of the material in an electrolyte gel, on a glass substrate and in a device was 40 %, 20 % and 13 % respectively. The fluorophore further underwent two near-simultaneous electrochemical oxidations. The first oxidation resulted in a 1000 nm red shift in the absorption to broadly absorb in the NIR, corresponding to the intervalence charge transfer (IVCT). Whereas the second oxidation led to a perceived green color at 715 nm with the extinction of the NIR absorbing IVCT. Owing to the dissymmetry of the fluorophore along with its two unique oxidation sites, the IVCT gives rise to a mixed valence transfer charge (MVCT). The coloration efficiency of the fluorophore in both solution and a device was 1433 and 200 cm2 C-1, respectively. The fluorescence intensity could be reversibly modulated electrochemically. The photoemission intensity of the fluorophore was modulated with applied potential in an operating electrochromic/electrofluorochromic device. Both the dual electrochromic and the electrofluorochromic behavior of the fluorophore were demonstrated.

Boron-Nitrogen-Containing Benzene Valence Isomers.

Benzene is one of the most ubiquitous structural motifs in chemistry. The valence isomers of benzene have also attracted synthetic chemists' attention due to their unique structures, bonding, and reactivity. We have been investigating boron-nitrogen-containing benzene valence isomers via photoisomerization of 1,2-azaborines. In this contribution, we summarize recent developments of these highly strained BN-heterocyclic compounds including their synthesis, characterization, proposed mechanism of formation, and their potential applications.

Risky-Choice Framing Effects Result Partly From Mismatched Option Descriptions in Gains and Losses.

Textbook psychology holds that people usually prefer a certain option over a risky one when options are framed as gains but prefer the opposite when options are framed as losses. However, this pattern can be amplified, eliminated, or reversed depending on whether option descriptions include only positive information (e.g., "200 people will be saved"), only negative information (e.g., "400 people will not be saved"), or both. Previous studies suggest that framing effects arise only when option descriptions are mismatched across frames. Using online and student samples (Ns = 906 and 521), we investigated 81 framing-effect variants created from matched and mismatched pairs of 18 option descriptions (nine in each frame). Description valence or gist explained substantial variation in risk preferences (prospect theory does not predict such variation), but a considerable framing effect remained in our balanced design. Risky-choice framing effects appear to be partly-but not completely-the result of mismatched comparisons.

Positive and negative facial valence perception are modulated differently by eccentricity in the parafovea: Replication from KDEF to NimStim.

While perceiving the emotional state of others may be crucial for our behavior even when this information is present outside of central vision, emotion perception studies typically focus on central visual field. We have recently investigated emotional valence (pleasantness) perception across the parafovea (≤ 4°) and found that for briefly presented (200 ms) emotional face images (from the established KDEF image-set), positive (happy) valence was the least affected by eccentricity (distance from the central visual field) and negative (fearful) valence the most. Furthermore, we found that performance at 2° predicted performance at 4°. Here we tested (n = 37) whether these effects replicate with face stimuli of different identities from a different well-established image-set (NimStim). All our prior findings replicated and eccentricity-based modulation magnitude was smaller with NimStim (~ 16.6% accuracy reduction at 4°) than with KDEF stimuli (~ 27.3% reduction). Our current investigations support our earlier findings that for briefly presented parafoveal stimuli, positive and negative valence perception are differently affected by eccentricity and may be dissociated. Furthermore, our results highlight the importance of investigating emotions beyond central vision and demonstrate commonalities and differences across different image sets in the parafovea, emphasizing the contribution of replication studies to substantiate our knowledge about perceptual mechanisms.

Valence-specific EEG microstate modulations during self-generated affective states.

Introduction: This study aims to explore the temporal dynamics of brain networks involved in self-generated affective states, specifically focusing on modulating these states in both positive and negative valences. The overarching goal is to contribute to a deeper understanding of the neurodynamic patterns associated with affective regulation, potentially informing the development of biomarkers for therapeutic interventions in mood and anxiety disorders. Methods: Utilizing EEG microstate analysis during self-generated affective states, we investigated the temporal dynamics of five distinct microstates across different conditions, including baseline resting state and self-generated states of positive valence (e.g., awe, contentment) and negative valence (e.g., anger, fear). Results: The study revealed noteworthy modulations in microstate dynamics during affective states. Additionally, valence-specific mechanisms of spontaneous affective regulation were identified. Negative valence affective states were characterized by the heightened presence of attention-associated microstates and reduced occurrence of salience-related microstates during negative valence states. In contrast, positive valence affective states manifested a prevalence of microstates related to visual/autobiographical memory and a reduced presence of auditory/language-associated microstates compared to both baseline and negative valence states. Discussion: This study contributes to the field by employing EEG microstate analysis to discern the temporal dynamics of brain networks involved in self-generated affective states. Insights from this research carry significant implications for understanding neurodynamic patterns in affective regulation. The identification of valence-specific modulations and mechanisms has potential applications in developing biomarkers for mood and anxiety disorders, offering novel avenues for therapeutic interventions.

Enhanced Electrical Conductivity of Polyoxometalates by Bridging with Mixed-valent Multinuclear Platinum Complexes.

Polyoxometalates (POMs) are nanosized molecular metal oxide anion clusters with tuneable structures and functionalities, and they exhibit a redox chemistry and catalytic activity in multielectron redox processes. These are typically poor electrical conductors (< 10-10 Scm-1), which is attributed to negligible electronic interactions among anions in the solid state. Since the reduced electrons on the d0 metals in POMs are delocalized, electrical conductivity was improved when judicious pathways for the electrons were created by bridging the POMs. Utilized with the electronic interactions between bridging oxygen atoms with the highest occupied molecular orbital in the POMs and the metal dz2 orbitals in the multinuclear platinum complexes, and three mixed-valent assemblies were synthesized and characterized. Simply mixing Keggin-type or Dawson-type POMs with tetranuclear or trinuclear platinum complexes in solution afforded three single crystals, and all three compounds were paramagnetic with mixed oxidation states and better conductivities at room temperature than the parent compounds.

Silver Decoration of Vertically Aligned MoS2-MoOx Nanosheets: A Comprehensive XPS Investigation.

This study investigates the simultaneous decoration of vertically aligned molybdenum disulfide nanostructure (VA-MoS2) with Ag nanoparticles (NPs) and nitrogen functionalization. Nitrogen functionalization was achieved through physical vapor deposition (PVD) DC-magnetron sputtering using nitrogen as a reactive gas, aiming to induce p-type behavior in MoS2. The utilization of reactive sputtering resulted in the growth of three-dimensional silver structures on the surface of MoS2, promoting the formation of silver nanoparticles. A comprehensive characterization was conducted to assess surface modifications and analyze chemical and structural changes. X-ray photoelectron spectroscopy (XPS) showed the presence of silver on the MoS2 surface. Scanning electron microscopy (SEM) confirmed successful decoration with silver nanoparticles, showing that deposition time affects the size and distribution of the silver on the MoS2 surface.

Quantifying and normalizing the combined phytotoxicity of mixed-valence chromium in soil integrated by toxicity equivalence.

When Cr(VI) and Cr(III) coexist, the reasonable assessment of the combined toxicity of chromium in soil and its ecological risk is still not well resolved. In the present study, exogenous mixed concentration combinations were set up to determine the interaction and combined toxicity of Cr(VI) and Cr(III), which were quantified as measured total and resin extractable forms for dose-response experiments with barley root elongation. The concept of toxicity equivalence "α" (the ratio of toxicity intensity coefficient between Cr(VI) and Cr(III), which can be expressed as the relative toxic strength of Cr(VI) to Cr(III)) was proposed for the toxicity assessment of mixed-valence chromium in soil. The results showed that the dose-response relationship was determined more precisely by the extended independent action model (e-IA) than traditional models (e.g., concentration addition model), and the mutual antagonism for resin extractable form (Resin-Cr) was stronger than the measured total form (T-Cr). The values of toxicity equivalence (α) between coexisting Cr(VI) and Cr(III) as Resin-Cr and T-Cr were 0.74 and 160, respectively, which indicated Resin-Cr(III) had relatively stronger toxicity than Resin-Cr(VI), while T-Cr(III) was much less than T-Cr(VI). The α values between Cr(VI) and Cr(III) decreased with their more active forms (decreased to about 0.5% of the original), even as total concentration and activity in solutions, making a dialectical view of the toxicity of both in different forms necessary. Finally, the log-logistic models were developed, enabling mixed-valence Cr toxicity to be assessed from a unilateral perspective using the Cr(III) equivalence concentration (Cr(III)-eq). This work provided innovative ideas for ecological threshold studies for mixed-valence metals in soils.

Coastal aquatic pollutants degradation using ZnCo2O4 nanorods.

Water pollution has caused problems in coastal areas, rivers, lakes, and other important water sources around the world as a result of inappropriate waste management. Meanwhile, these pollutants are harmful to humans and aquatic life. Textile dye effluent methyl orange (MO) was used in this work for dye degradation studies employing nanocomposites. As a result, the importance of synthesizing pure ZnO and Co3O4 nanoparticles with composites of ZnCo2O4 (zinc cobaltite) nanorods in three various proportions (90:10, 75:25, and 50:50) is emphasized in this study. Many advanced approaches were used to assess the various features of these materials, including size and shape. Fourier transform infrared (FT-IR) spectroscopy was used to determine the vibrational modes of the materials. The absorption measurements were then carried out using UV-vis spectroscopic techniques, and the photocatalytic breakdown of MO was done under visible light irradiation. The findings revealed that pure materials were inadequate for visible light activity, resulting in decreased degradation efficiencies. Spinel cobaltite structures have potential degradation efficiency under visible light, while ZnCo2O4 (50:50) catalyst has superior degradation efficiency of 59.8% over MO. The crystallite size, morphology, functional group, absorption wavelength, and band gap all play important roles in enhancing the material's photocatalytic activity under visible light. Meanwhile, ZnCo2O4 spinel structures are crucial for increasing charge carriers and reducing electron-hole recombination. As a result, zinc cobaltite minerals are widely used in industrial dye degradation applications.