Advancements and Challenges in the Application of Metal-Organic Framework (MOF) Nanocomposites for Tumor Diagnosis and Treatment.

Nanoscale metal-organic frameworks (MOFs) offer high biocompatibility, nanomaterial permeability, substantial specific surface area, and well-defined pores. These properties make MOFs valuable in biomedical applications, including biological targeting and drug delivery. They also play a critical role in tumor diagnosis and treatment, including tumor cell targeting, identification, imaging, and therapeutic methods such as drug delivery, photothermal effects, photodynamic therapy, and immunogenic cell death. The diversity of MOFs with different metal centers, organics, and surface modifications underscores their multifaceted contributions to tumor research and treatment. This review is a summary of these roles and mechanisms. The final section of this review summarizes the current state of the field and discusses prospects that may bring MOFs closer to pharmaceutical applications.

Structure-Property Relationship of Defect-Trapped Pt Single-Site Electrocatalysts for the Hydrogen Evolution Reaction.

Single-site catalysts (SSCs) have attracted significant research interest due to their high metal atom utilization. Platinum single sites trapped in the defects of carbon substrates (trapped Pt-SSCs) have been proposed as efficient and stable electrocatalysts for the hydrogen evolution reaction (HER). However, the correlation between Pt bonding environment, its evolution during operation, and catalytic activity is still unclear. Here, a trapped Pt-SSC is synthesized by pyrolysis of H2PtCl6 chemisorbed on a polyaniline substrate. In situ heated scanning transmission electron microscopy and temperature-dependent X-ray photoelectron spectroscopy clarify the thermally induced structural evolution of Pt during pyrolysis. The results show that the nitrogen in polyaniline coordinates with Pt ions and atomically disperses them before pyrolysis and traps Pt sites at pyridinic N defects generated during the substrate graphitization. Operando X-ray absorption spectroscopy confirms that the trapped Pt-SSC is stable at the HER working potentials but with inferior electrocatalytic activity compared with metallic Pt nanoparticles. First principle calculations suggest that the inferior activity of trapped Pt-SSCs is due to their unfavorable hydrogen chemisorption energy relative to metallic Pt(111) surfaces. These results further the understanding of the structure-property relationship in trapped Pt-SSCs and motivate a detailed techno-economic analysis to evaluate their commercial applicability.

Children with autism spectrum disorder perform comparably to their peers in a parent-child cooperation task.

This study investigates whether and how parent's cooperation affects child's cooperation, and whether that differs between children with/without autism spectrum disorder (ASD). The experiment involved a cooperative key-pressing task completed first by parent-parent dyads and then by parent-child dyads, meanwhile brain activity in the right frontal-parietal cortex of dyad partners was measured synchronously. The results showed the following: ASD children exhibited performance comparable to those of their peers, as was the level of brain synchronization with their parents, which was mainly due to parents with ASD children tending to adjust their own response patterns to match those of their children. These findings suggest that parents can somewhat actively mitigate the lower interpersonal synchronization ability of ASD children, in behavioral or/and neural level.

The modulation of pain in reward processing is reflected by increased P300 and delta oscillation.

Pain elicits the desire for a reward to alleviate the unpleasant sensation. This may be a consequence of facilitated neural activities in the reward circuit. However, the temporal modulation of pain on reward processing remains unclear. We addressed this issue by recording electroencephalogram when participants received win or loss feedback in a simple gambling task. Pain treatment was conducted on 33 participants with topical capsaicin cream and on 33 participants with hand cream as a control. Results showed that pain generally increased the P300 amplitude for both types of feedback but did not affect feedback-related negativity (FRN). A significant interaction effect of treatment (painful, non-painful) and outcome (win, loss) was observed on delta oscillation as pain only enhanced the power of win feedback. In addition, the FRN and theta oscillation responded more to loss feedback, but this effect was unaffected by pain. These findings indicate that pain may enhance secondary value representation and evaluation processes of rewards, but does not influence primary distinction of reward or reward expectation. The temporal unfolding of how pain affects reward-related neural activities highlights the prominent impact of pain on high-level cognitive processes associated with reward.

Incidental physical pain reduces brain activities associated with affective social feedback and increases aggression.

Physical pain may lead to aggressive behavior in a social context. However, it is unclear whether this is related to changes of social information processing. Thus, this study aimed to investigate the neural mechanisms underlying pain-induced aggression using functional magnetic resonance imaging. In the experiment, 59 healthy participants were recruited: 31 were treated with topical capsaicin cream (pain group) and 28 with hand cream (control group). Participants completed a social network aggression task, during which they underwent two phases: feedback processing and attack exerting. The results revealed that participants in the pain group exhibited more aggression than those in the control group. During the feedback-processing phase, physical pain reduced brain activation in the right insula, left orbitofrontal cortex and anterior cingulate cortex, which typically exhibited stronger activation in response to negative (and positive) vs neutral social feedback in the control group. However, during the attack-exerting phase, pain did not significantly alter the activation of the dorsolateral prefrontal cortex. These findings suggest that pain increased aggression, while before that, it suppressed brain activities of the salience network involved in the process of salient social information and the value system associated with the value representation of social events.

Elucidating the Formation and Structural Evolution of Platinum Single-Site Catalysts for the Hydrogen Evolution Reaction.

Platinum single-site catalysts (SSCs) are a promising technology for the production of hydrogen from clean energy sources. They have high activity and maximal platinum-atom utilization. However, the bonding environment of platinum during operation is poorly understood. In this work, we present a mechanistic study of platinum SSCs using operando, synchrotron-X-ray absorption spectroscopy. We synthesize an atomically dispersed platinum complex with aniline and chloride ligands onto graphene and characterize it with ex-situ electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, X-ray absorption near-edge structure spectroscopy (XANES), and extended X-ray absorption fine structure spectroscopy (EXAFS). Then, by operando EXAFS and XANES, we show that as a negatively biased potential is applied, the Pt-N bonds break first followed by the Pt-Cl bonds. The platinum is reduced from platinum(II) to metallic platinum(0) by the onset of the hydrogen-evolution reaction at 0 V. Furthermore, we observe an increase in Pt-Pt bonding, indicating the formation of platinum agglomerates. Together, these results indicate that while aniline is used to prepare platinum SSCs, the single-site complexes are decomposed and platinum agglomerates at operating potentials. This work is an important contribution to the understanding of the evolution of bonding environment in SSCs and provides some molecular insights into how platinum agglomeration causes the deactivation of SSCs over time.

Simultaneous determination of molar degree of substitution and its distribution fraction, degree of acetylation in hydroxypropyl chitosan by 1H NMR spectroscopy.

Under the assistance of 13C NMR and 1H-13C HSQC, we develop a novel 1H NMR assay for the substitution sites and degrees in hydroxypropyl chitosan (HPCS) by optimizing sample preparation and measurement method. We find that the chemical shift of HOD peak increases linearly with the increase of DCl concentration but declines with the rise of measurement temperature. According to the regression line, the HOD peak could be moved to a desired position of non-interference with other peaks by changing DCl concentration. Other DCl-responsive peaks are found and elucidated. Accordingly, the substitution fraction (NH2-substitution and OH-substitution) and the degree of acetylation are well discriminated and determined. The total molar degree of substitution (MS) obtained is basically consistent with those of elemental analysis and the existing NMR methods. This structural analysis is extendable to other amino-containing saccharides. The 1H NMR method could be used widely in acid-soluble polysaccharides and their derivatives.

Does Cardiorespiratory Fitness Influence the Effect of Acute Aerobic Exercise on Executive Function?

BACKGROUND: The beneficial effects of acute exercise on executive function have been well-documented, but the influence of cardiorespiratory fitness on this effect requires further investigations, especially using imaging technique. This study aimed to examine the effects of cardiorespiratory fitness on acute exercise-induced changes on behavioral performance and on functional brain activation. METHOD: Based on their cardiorespiratory fitness level, 62 participants ranked in the top and bottom of the maximum oxygen consumption (VO2 max) were finally selected and allocated to high-fit group or low-fit group. Both groups were asked to complete the Stroop task after 30 min of aerobic exercise and chair-seated rest (control session). Among them, 26 participants were randomly selected and asked to undergo the Functional Magnetic Resonance Imaging (fMRI). RESULTS: Behavioral results showed that individuals responded significantly faster after exercise than those in the control session. The fMRI results revealed a significant interaction effects of Group by Session in brain regions including anterior cingulate cortex (ACC) and bilateral dorsal lateral prefrontal cortex (DLPFC). For the ACC, activation in the high-fit group was significantly decreased after aerobic exercise compared to those in the control session; whereas an increased activation was noticed in the low-fit group. Regarding to the bilateral DLPFC, activation in high-fit group was significantly decreased after exercise compared to those in the control session, while no significant differences were found in the low-fit group. In addition, for the post-exercise session, a significant positive correlations between activation of the ACC and left DLPFC in the high-fit group was observed. There was a significant negative correlation between activation of the ACC and reaction time in the congruent condition after exercise in the low-fit group. CONCLUSION: Findings further clarify the neurophysiological processes of acute exercise-induced changes in cognitive performance as they suggest that cardiorespiratory fitness is an important factor which influences changes in brain activation patterns in response to acute aerobic exercises.

Different strategies, distinguished cooperation efficiency, and brain synchronization for couples: An fNIRS-based hyperscanning study.

INTRODUCTION: Individuals may employ different strategies when cooperating with others. For example, when two participants are asked to press buttons simultaneously, they may press the buttons as quickly as possible (immediate response strategy) or press them in a delayed pattern (delayed response strategy). Despite recognition of interpersonal brain synchronization (IBS) as a fundamental neural mechanism of cooperation, it remains unclear how various strategies influence cooperative behavior and its neural activities. METHODS: To address this issue, 43 married couples were recruited to complete a button-press cooperative task, during which IBS was recorded by functional near-infrared spectroscopy hyperscanning. RESULTS: Behavioral results showed that couples who adopted a delayed response strategy performed better than those who adopted an immediate response strategy and those without any obvious strategy, and a new measure (cooperation coefficient) was used to index the level of cooperation. In addition, stronger IBS in the right frontal cortex was observed in the delayed response condition. The greater couples' perceived parenting stress, the more likely they were to perform well in tasks and the stronger their brain synchronization, since they tended to choose the delayed response strategy. CONCLUSION: The delayed response strategy may better unify dyad partners' response modes, trigger synchronized psychological processes, and enable their brains to become synchronized. The study extends understanding of cooperation by comparing the contributions of different strategies underlying cooperative behavior with corresponding neural evidence.

Pain modulates neural responses to reward in the medial prefrontal cortex.

Pain has been found to promote reward-seeking behaviors, which might be a consequence of modulated brain activities in the reward neural circuitry in a painful state. The present study investigated how pain affected reward processing and reward-related neural activities using fMRI technique. A total of 50 healthy participants were recruited and used for data analyses, with half being treated with topical capsaicin cream and the other half with hand cream (treatment: pain or control). The participants were asked to perform a card-guessing game when their brain activities responding to feedbacks (outcome: win or loss) were recorded. Behavioral results showed that participants in pain group overestimated their correct choices in the card-guess game. Whole-brain fMRI analysis revealed that the main effect of outcome (win vs. loss) activated a typical network of the reward neural circuitry, including the medial prefrontal cortex (mPFC) and the bilateral nucleus accumbens (NAcc). Importantly, the region of interest analysis revealed a significant interaction of treatment and outcome in the mPFC, with increased mPFC neural activity responding to win outcome in pain condition. Moreover, the functional connectivity between the mPFC and the NAcc was decreased in pain condition. We conclude that the pain-induced modulation of the mPFC activity could result in alterations of both the emotional response to and the cognitive evaluation of reward.

Facile One-Pot Synthesis of Bimetallic Co/Mn-MOFs@Rice Husks, and its Carbonization for Supercapacitor Electrodes.

Novel hybrid nanomaterials comprising metal-organic framework compounds carbonised in the presence of biomass material derived from rice husk have been investigated as a new class of sustainable supercapacitor materials for electrochemical energy storage. Specifically, two synthetic routes were employed to grow Co/Mn metal-organic framework compounds in the channels of rice husks, which had been activated previously by heat treatment in air at 400 °C to produce a highly porous network. Pyrolysis of these hybrid materials under nitrogen at 700 °C for 6 h produced metal-containing phases within the nanocarbon, comprising intimate mixtures of Co, MnO and CoMn2O4. The materials thus produced are characterized in detail using a range of physical methods including XRD, electron microscopy and X-ray photoelectron spectroscopy. The synthetic pathway to the metal-organic framework compound is shown to influence significantly the physical properties of the resulting material. Electrochemical evaluation of the materials fabricated revealed that higher specific capacitances were obtained when smaller crystallite sized bimetallic Co/Mn-MOFs were grown inside the rice husks channels compared to larger crystallite sizes. This was in-part due to increased metal oxide loading into the rice husk owing to the smaller crystallite size as well as the increased pseudocapacitance exhibited by the smaller crystallite sizes and increased porosity.

Dynamic interpersonal neural synchronization underlying pain-induced cooperation in females.

Individuals in pain are motivated to be cooperative in social interaction. Yet, there has been little research on how pain dynamically affects cooperation at a neural level. The present study investigated the cooperative behavior under acute physical pain by asking dyads to complete three blocks of button-press cooperative task, while neural activities were recorded simultaneously on each subject by the fNIRS-based hyperscanning. Results showed that individuals in pain improved their cooperation rate across task blocks. Accordingly, increased interpersonal neural synchronization (INS) was found at the left prefrontal cortex in second block, whereas increased INS was found at the right prefrontal cortex and the right parietal cortex in third block compared to the first block. Moreover, the change of INS in right parietal cortex was positively correlated with subjective pain rating in the pain treatment group. In addition, dynamic interpersonal neural networks were identified in painful condition with increasing frontoparietal networks across time. By uncovering dissociative neural processes involved in how pain affects cooperation in social interaction, the present work provides the first interbrain evidence to highlight the sociality of pain on social interaction in perspective of motivational aspect of pain.

Grob-Type Fragmentation Releases Paracyclophane Ring Strain in a Late-Stage Precursor of Haouamine A.

A ketene [2 + 2]-addition, an intramolecular aldol reaction, a Suzuki-Miyaura coupling, and a chemoselective lactam reduction were used to prepare a late-stage precursor of haouamine A. Exposure to acid led to a Grob-type fragmentation of the strained 3-aza[7]paracyclophane ring, followed by a tandem Pictet-Spengler reaction of the intermediate iminium ion and conversion to a novel 1,4a-propanocyclopenta[ b]pyridine. This cascade reaction might also be relevant for the mechanism of action of the natural product.

Reminders of Mortality Alter Pain-Evoked Potentials in a Chinese Sample.

Pain is of evolutionary importance to human survival. However, the perception of pain could be changed when death-related thoughts are accessible. Although the influence of mortality salience (MS) on pain processing has been investigated in Westerners recently, it is unclear whether this effect is constrained by specific culture context since humans may employ cultural worldviews to defend the existence problem. The current study tested whether and how MS affected pain processing in a Chinese male sample. We primed participants with sentences indicating MS or negative affect (NA) on either of two days. Both before and after the priming, event-related potentials (ERPs) elicited by painful and non-painful electrical stimulations were recorded. Results showed that pain-evoked potentials were identified as an early negative complex N60-P90-N130 and a late positivity P260. Pain-evoked N130 after MS priming was larger than that after NA priming. Meanwhile, pain-evoked P260 decreased after MS priming but not after NA priming. These findings indicate that reminders of mortality affect both early sensory and late cognitive neural responses related to physical pain. Although previous studies reporting an increased effect of MS on perceived pain intensity in Westerners, we found an unchanged or possibly reduced effect in Chinese. Thus, the current work provides insight into a culture-sensitive perspective on how pain processing would be modulated when existential problem occurs.

Distinct oxytocin effects on belief updating in response to desirable and undesirable feedback.

Humans update their beliefs upon feedback and, accordingly, modify their behaviors to adapt to the complex, changing social environment. However, people tend to incorporate desirable (better than expected) feedback into their beliefs but to discount undesirable (worse than expected) feedback. Such optimistic updating has evolved as an advantageous mechanism for social adaptation. Here, we examine the role of oxytocin (OT)-an evolutionary ancient neuropeptide pivotal for social adaptation-in belief updating upon desirable and undesirable feedback in three studies (n = 320). Using a double-blind, placebo-controlled between-subjects design, we show that intranasally administered OT (IN-OT) augments optimistic belief updating by facilitating updates of desirable feedback but impairing updates of undesirable feedback. The IN-OT-induced impairment in belief updating upon undesirable feedback is more salient in individuals with high, rather than with low, depression or anxiety traits. IN-OT selectively enhances learning rate (the strength of association between estimation error and subsequent update) of desirable feedback. IN-OT also increases participants' confidence in their estimates after receiving desirable but not undesirable feedback, and the OT effect on confidence updating upon desirable feedback mediates the effect of IN-OT on optimistic belief updating. Our findings reveal distinct functional roles of OT in updating the first-order estimation and second-order confidence judgment in response to desirable and undesirable feedback, suggesting a molecular substrate for optimistic belief updating.

Serotonin transporter polymorphism alters citalopram effects on human pain responses to physical pain.

Humans exhibit substantial inter-individual differences in pain perception, which contributes to variability in analgesic efficacy. Individual differences in pain sensitivity have been linked with variation in the serotonin transporter gene (5-HTTLPR), and selective serotonin reuptake inhibitors (SSRIs) such as citalopram have been increasingly used as treatments for multiple pain conditions. We combined genotyping, pharmacological challenge, and neuroimaging during painful electrical stimulation to reveal how serotonin genetics and pharmacology interact to influence pain perception and its underlying neurobiological mechanisms. In a double-blind, placebo-controlled procedure, we acutely administrated citalopram (30mgpo) to short/short (s/s) and long/long (l/l) healthy male 5-HTTLPR homozygotes during functional MRI with painful and non-painful electrical stimulation. 5-HTTLPR genotype modulated citalopram effects on pain-related brain responses in the thalamus, cerebellum, anterior insula, midcingulate cortex and inferior frontal cortex. Specifically, citalopram significantly reduced pain-related brain responses in l/l but not in s/s homozygotes. Moreover, the interaction between 5-HTTLPR genotype and pain-related brain activity was a good predictor of the citalopram-induced reductions in pain reports. The genetic modulations of citalopram effects on brain-wide pain processing were paralleled by significant effects on the Neurological Pain Signature, a multivariate brain pattern validated to be sensitive and specific to physical pain. This work provides neurobiological mechanism by which genetic variation shapes brain responses to pain perception and treatment efficacy. These findings have important implications for the types of individuals for whom serotonergic treatments provide effective pain relief, which is critical for advancing personalized pain treatment.

Allelic variation in 5-HTTLPR and the effects of citalopram on the emotional neural network.

BACKGROUND: Selective serotonin reuptake inhibitors (SSRIs), such as citalopram, which selectively block serotonin transporter (5-HTT) activity, are widely used in the treatment of depression and anxiety disorders. Numerous neuroimaging studies have examined the effects of SSRIs on emotional processes. However, there are considerable inter-individual differences in SSRI effect, and a recent meta-analysis further revealed discrepant effects of acute SSRI administration on neural responses to negative emotions in healthy adults. AIMS: We examined how a variant of the serotonin-transporter polymorphism (5-HTTLPR), which affects the expression and function of 5-HTT, influenced the acute effects of an SSRI (citalopram) on emotion-related brain activity in healthy adults. METHOD: Combining genetic neuroimaging, pharmacological technique and a psychological paradigm of emotion recognition, we scanned the short/short (s/s) and long/long (l/l) variants of 5-HTTLPR during perception of fearful, happy and neutral facial expressions after the acute administration of an SSRI (i.e. 30 mg citalopram administered orally) or placebo administration. RESULTS: We found that 5-HTTLPR modulated the acute effects of citalopram on neural responses to negative emotions. Specifically, relative to placebo, citalopram increased amygdala and insula activity in l/l but not s/s homozygotes during perception of fearful faces. Similar analyses of brain activity in response to happy faces did not show any significant effects. CONCLUSIONS: Our combined pharmacogenetic and functional imaging results provide a neurogenetic mechanism for discrepant acute effects of SSRIs.

A multi-functional oil-water separator from a selectively pre-wetted superamphiphobic paper.

A multi-functional oil-water separator is prepared from a paper towel spray coated with superamphiphobic (i.e., superhydrophobic and superoleophobic) nanoparticles. After the separator is pre-wetted with ethanol, followed by water, water can be removed from the light oil-water mixture and emulsions by gravity with high separation efficiency (99.9%) and separation flux. Vice versa, heavy oil can be removed by gravity on an ethanol-oil pre-wetted SA-paper.

Interaction between oxytocin receptor polymorphism and interdependent culture values on human empathy.

Recent evidence suggests that the association between oxytocin receptor polymorphism (OXTR rs53576) and emotion-related behavioral/psychological tendencies differs between individuals from East Asian and Western cultures. What remains unresolved is which specific dimension of cultural orientations interacts with OXTR rs53576 to shape these tendencies and whether such gene × culture interactions occurs at both behavioral and neural level. This study investigated whether and how OXTR rs53576 interacts with interdependence-a key dimension of cultural orientations that distinguish between East Asian and Western cultures-to affect human empathy that underlies altruistic motivation and prosocial behavior. Experiment 1 measured interdependence, empathy trait and OXTR rs53576 genotypes of 1536 Chinese participants. Hierarchical regression analyses revealed a stronger association between interdependence and empathy trait in G allele carriers compared with A/A homozygotes of OXTR rs53576. Experiment 2 measured neural responses to others' suffering by scanning A/A and G/G homozygous of OXTR rs53576 using functional magnetic resonance imaging. Hierarchical regression analyses revealed stronger associations between interdependence and empathic neural responses in the insula, amygdala and superior temporal gyrus in G/G compared with A/A carriers. Our results provide the first evidence for gene × culture interactions on empathy at both behavioral tendency and underlying brain activity.

Challenging emotional prejudice by changing self-concept: priming independent self-construal reduces racial in-group bias in neural responses to other's pain.

Humans show stronger empathy for in-group compared with out-group members' suffering and help in-group members more than out-group members. Moreover, the in-group bias in empathy and parochial altruism tend to be more salient in collectivistic than individualistic cultures. This work tested the hypothesis that modifying self-construals, which differentiate between collectivistic and individualistic cultural orientations, affects in-group bias in empathy for perceived own-race vs other-race pain. By scanning adults using functional magnetic resonance imaging, we found stronger neural activities in the mid-cingulate, left insula and supplementary motor area (SMA) in response to racial in-group compared with out-group members' pain after participants had been primed with interdependent self-construals. However, the racial in-group bias in neural responses to others' pain in the left SMA, mid-cingulate cortex and insula was significantly reduced by priming independent self-construals. Our findings suggest that shifting an individual's self-construal leads to changes of his/her racial in-group bias in neural responses to others' suffering.