Modulation Of Interactions Research Articles

Modulation of d-Orbital Interactions in Dual-Atom Catalysts for Enhanced Polysulfide Anchoring and Kinetics in Lithium-Sulfur Batteries.

Modulating the electronic structure is essential for improving the anchoring and catalytic capabilities of catalysts in lithium-sulfur batteries (LSBs). This study delves into the modulation of d-orbitals in transition metal dual-atom catalysts (DACs) supported by boron nitride and graphene (BNC) hybrid sheets for LSBs. This study reveals that the d-band center of the DACs, a key determinant of material chemical properties, is primarily determined by the electronic configuration of the dyz and dx2-y2 orbitals. Furthermore, the interaction between dz2 of transition metals and S_3 p orbitals is critical for the binding strength of LiPSs. By understanding these interactions, the functionality of DACs can be customized for optimal performance in LSBs. For example, the MnCrBNC catalyst with 10 d-electrons exhibits the optimal d-band center and demonstrates exceptional LiPSs binding capability, the lowest Li2S decomposition energy barrier, and the lowest Gibbs free energy of reaction for the rate-determining step of sulfur reduction. This study elucidates the fundamental mechanisms for designing high-performance LSB catalysts through electronic structure modulation.

Synchronous Modulation of H-bond Interaction and Steric Hindrance via Bio-molecular Additive Screening in Zn Batteries.

In addressing challenges such as side reaction and dendrite formation, electrolyte modification with bio-molecule sugar species has emerged as a promising avenue for Zn anode stabilization. Nevertheless, considering the structural variability of sugar, a comprehensive screening strategy is meaningful yet remains elusive. Herein, we report the usage of sugar additives as a representative of bio-molecules to develop a screening descriptor based on the modulation of the hydrogen bond component and electron transfer kinetics. It is found that xylo-oligosaccharide (Xos) with the highest H-bond acceptor ratio enables efficient water binding, affording stable Zn/electrolyte interphase to alleviate hydrogen evolution. Meanwhile, sluggish reduction originated from the steric hindrance of Xos contributes to optimized Zn deposition. With such a selected additive in hand, the Zn||ZnVO full cells demonstrate durable operation. This study is anticipated to provide a rational guidance in sugar additive selection for aqueous Zn batteries.

Exciting the Higgs Mode in a Strongly Interacting Fermi Gas by Interaction Modulation.

We study the Higgs mode of a strongly interacting Fermi gas in the crossover regime between a fermionic and bosonic superfluid. By periodically modulating the interaction strength of the gas, we parametrically excite the Higgs mode and study its resonance frequency and line width as a function of both interaction strength and temperature. We find that the resonance frequency at low temperature agrees with a local-density approximation of the pairing gap. Both frequency and line width do not exhibit a pronounced variation with temperature, which is theoretically unexpected, however, in qualitative agreement with a different recent study.

DNA logic gate for cancer cells identification, detection, and modulation of cell–cell interactions

The precise detection of cancer cells and modulation of cell–cell interactions would be highly desired for noninvasive and nontoxic cancer treatments but it remains challenging due to the existence of biomarkers on both normal and tumor cells. In this work, we engineered a logic-gated DNA molecular machine incorporating a membrane protein aptamer and an extracellular acid responsive split i-motif for the precise identification and detection of cancer cells, as well as the mediation of cell–cell interactions. In this system, only in the presence of both the membrane protein and protons, the logic-gated DNA molecular machine is activated to perform the “AND” logic operation to induce catalytic hairpin assembly (CHA) on the electrode, leading to the formation of G-quadruplex/hemin and the generation of an amplified electrochemical signal. On the other hand, the formed “AND” logic could hybridize with the DNA fragment on T-cell, effectively shorting the distance between T-cell and cancer cells. Benefiting from the DNA logic gate and CHA, this strategy could not only precisely identify cancer cells, but also show a sensitive analysis of cancer cells with a detection limit of 15 cells/mL. The logic-gated DNA molecular machine achieved the identification of cancer cells and modulation of intercellular interactions, providing a new idea for precise disease diagnosis and therapy.

The long non-coding RNA GAS5 contributes to the suppression of inflammatory responses by inhibiting NF-κB activity.

Nuclear factor kappa B (NF-κB) is a key regulator of immune and inflammatory responses. Glucocorticoid drugs (GC) act through the glucocorticoid receptor (GR) as immunosuppressant also in pediatric patients inhibiting NF-κB activity. The long non-coding RNA GAS5 interacts with the GR, influencing GC activity. No data on the role of GAS5 on GR-dependent inhibition of NF-κB activity have been published. This study investigated the impact of GAS5 on NF-κB activity in HeLa cells overexpressing GAS5, both under basal conditions and during GC treatment. The study used EMSA, RNA-immunoprecipitation (RIP), Western blotting, and bioinformatic analyses to assess NF-κB DNA binding, GAS5-p65 interaction, and NF-κB signaling pathway modulation. GAS5 overexpression increased NF-κB DNA binding activity in untreated cells. RNA-IP confirmed a direct interaction between GAS5 and the NF-κB subunit p65, suggesting a potential regulatory mechanism. GAS5 overexpression led to downregulation of NF-κB target genes, TNF-α, and NR3C1. GC treatment reduced NF-κB DNA binding activity in GAS5-overexpressing cells, indicating a potential synergistic effect. Furthermore, GAS5 overexpression increased IκB levels and reduced p-p65/pan-p65 levels during GC treatment. GAS5 appears to modulate NF-κB activity in a complex manner, influencing both basal and GC-induced signaling. The interaction between GAS5, GCs, and NF-κB is multi-faceted, and further research is needed to fully elucidate the underlying mechanisms. These findings suggest that GAS5 could be a potential target for personalized therapy, particularly in pediatric patients with inflammatory conditions.

Bifunctional fluorine doped Ru/RuO2 clusters with dynamic electron modification and strong metal-support interaction boost proton exchange membrane water electrolyzer

The sluggish kinetics and inherent instability over the Ru/RuO2 clusters are still enormous challenges in proton exchange membrane (PEM) water electrolyzer. Herein, we innovatively report synergistic modulation of dynamic electron modification and strong metal-support interaction (SMSI) to activate and stabilize bifunctional fluorine doped Ru/RuO2 clusters anchored on carbon nanotube (CNT), thus achieving efficient and stable acidic overall water splitting. Theoretical and experimental studies found that surface metal-fluorine modification layer could dynamically regulate the interfacial electronic environment to stabilize and activate multiple active Ru species; and the SMSI between Ru/RuO2 cluster and CNT maintains stable electronic environment for dynamic electron modification and avoids migrating or shedding of active species in acidic environment. Therefore, the PEM electrolyzer assembled with optimal F5.5-Ru/RuO2@CNT can operate stably for 100 h at a high current density of 100 mA cm−2, which is the first time that bifunctional Ru-based nanocatalysts applied to PEM device at a high current density.

An experimental and computational investigation of the cyclopentene-containing peptide-derived compounds: focus on pseudo-cyclic motifs via intramolecular interactions.

Conformational flexibility is one of the main disadvantages of peptide-based compounds. We focus on their molecular 'chameleonicity' related to forming pseudo-cyclic motifs via modulation of weak intramolecular interactions. It is an appealing strategy for controlling equilibrium between the polar open and the nonpolar closed conformations. Within this context, we report here the crystal structure of the (R)-(2-tert-butoxycarbonyl)amino-1-oxo-3-phenyl)propyl)-1-cyclopentene (1), synthesis of which in high yield was achieved by a facile multi-step protocol. Our Cambridge Structural Database (CSD) overview for the peptide-based crystals revealed the exclusivity of this compound from the viewpoint of the unusual pseudo-bicyclic system via C-H…O and C-O…π interactions, in which cyclopentene shields the amide bond. Notably, cyclopentene as a bioisostere of proline is an appealing scaffold in medicinal chemistry. An extensive combined experimental and computational study provided more profound insight into the supramolecular landscape of 1 with respect to similar derivatives deposited in the CSD, including the tendency of cyclopentene for the generation of pseudo-cyclic motifs through weak H-bonding and π-based intramolecular interactions. These weak interactions have been examined by either the quantum theory of 'atoms-in-molecules' (QTAIM) or complex Hirshfeld surface methodology, including enrichment ratios, molecular electrostatic potential surfaces and energy frameworks. In all analysed crystals, all types of H-bonded motifs involving cyclopentene are formed at all levels of supramolecular architecture. A library of cyclopentene-based H-bonding synthons is provided. A molecular docking study depicted vital interactions of cyclopentene with key amino acid residues inside the active sites of two prominent protein kinases, uncovering the therapeutic potential of 1 against breast cancer. To a large extent, dispersion forces have significance in stabilizing the supramolecular structure of both ligand and bio-complex ligand-protein. Finally, the satisfactory in silico bio-pharmacokinetic profile of 1 related to drug-likeness and blood-brain barrier permeation was also revealed.

Meta-substituted thienoviologen with enhanced radical stability via π-π interaction modulation for neutral aqueous organic flow batteries

The aqueous organic redox flow batteries (AORFBs) are recognized as the most promising large-scale storage technology for long-duration energy storage (LDES). Although viologen derivatives are widely used as anolyte materials for AORFBs, their practical application is strongly limited by weak conjugation and unstable radicals. Here, we present a novel thienoviologen derivative, [(NPr)2SV]Cl4, achieved utilizing a meta-substitution approach based on the pristine viologen derivatives ( [(NPr)2V]Cl4). Compared to other ortho- and para-substitution methods, this strategy features a locked plane configuration (0.14°), effectively regulating π-π interactions and suppressing reactivity between radical and oxygen, which is confirmed via X-ray single-crystal structural analyses, spectroscopy techniques, molecular dynamics simulation accompanied by linear ion trap mass spectrometry experiments. Additionally, the meta-substituted [(NPr)2SV]Cl4 significantly improves water solubility (2.39 M), enhances aromaticity, and extends radical lifetime compared with para-substituted [(NPr)2TV]Cl4. Consequently, the cycling stability of the [(NPr)2SV]Cl4-based AORFB over 2500 cycles is 4.1 times higher than that of [(NPr)2TV]Cl4. Furthermore, the 0.5 M battery delivers an impressive 99.83% capacity retention during 200 cycles and a power density of 147 mW cm-2.

Aggregation-Disruption-Induced Multi-Scale Mediating Strategy for Anticoagulation in Blood-Contacting Devices.

Minimally invasive blood-contacting interventional devices are increasingly used to treat cardiovascular diseases. However, the risk of device-related thrombosis remains a significant concern, particularly the formation of cycling thrombi, which pose life-threatening risks. To better understand the interactions between these devices and blood, the initial stages of coagulation contact activation on extrinsic surfaces areinvestigated. Direct force measurements reveals that activated contact factors stimulate the intrinsic coagulation pathway and promote surface crosslinking of fibrin. Furthermore, fibrin aggregation is disrupted by surface-grafted inhibitors, as confirmed by ex vivo coagulation tests. An engineered serum protein with zwitterion grafts to resist the deposition of biological species such as fibrin, platelets, and red blood cells is also developed. Simultaneously, a protease inhibitor-based coacervate is incorporated into the coating to inhibit the intrinsic pathway effectively. The loaded coacervate can be released and reloaded through modulation of catechol-amine interactions, facilitating material regeneration. The strategy offers a novel multi-scale mediation strategy that simultaneously inhibits nanoscale coagulation factors and resists microscale thrombus aggregation, providing a long-term solution for anticoagulation in blood-contacting devices.

Hydrophobic surface modification and morphology tuning of supported KNiMoS-based catalyst for synergistically enhanced higher alcohols synthesis via CO hydrogenation

MoS2-based catalysts have gained significant attention in higher alcohols synthesis (HAS) via CO hydrogenation. However, the water–gas shift (WGS) to produce CO2 in HAS is undesirable reaction, which will reduce the efficiency of carbon utilization. Here, we provide a facile strategy with hydrophobic surface modification and metal-support interaction modulation to design a series of KNiMoS/MgAl catalysts. The organic modified SiO2 shell with excellent hydrophobicity effectively shortens the residence of water formed in HAS, and further suppress the generation of CO2 and low-chain hydrocarbons. Moreover, the moderate metal-support interaction between MoS2-based active species and MgAl support can regulate the dispersion and sulfidation extent of MoS2 slabs to provide more active sites for alcohol formation. The MoS2 slabs with predominant double-layer structure enhance the C–C propagation and CO insertion in HAS. And as a result, the optimal KNiMoS/MgAl@Si(c)-5 achieves total alcohols selectivity of 74.7 %, C2+OH selectivity of 85.8 % in total alcohols, and C2+ alcohols space–time yield of 107.8 mg gcat-1h−1, where C2+ alcohols space–time yield is 3.50 and 2.71 times than those on KNiMoS/MgAl(H) and KNiMoS/MgAl, respectively. Notably, the total selectivity of CO2 and hydrocarbons is less than 23.2 %, and selectivity ratio of C2-4OH to methanol can be overturned from 1.9 to 6.0. The dependence of HAS performance on the morphology of MoS2 slabs were also demonstrated to get insight into the structure-performance relationship. This work provides a facile strategy with tunable hydrophobic surface and metal-support interaction of MoS2-based catalysts for further improvement of catalytic performance.

Insights into molecular characterization of NOD1-RIPK interaction and transcriptional modulation in response to LPS in spotted snakehead, Channa punctata (Bloch, 1793)

NOD1, plays a pivotal role in immune responses against bacterial as well as viral invasions. While the downstream signaling pathway of NOD1 is well understood in mammals, its characterization in lower vertebrates remains elusive. In present study, an effort was made to identify and characterize downstream signaling cascade of NOD1 in response to LPS, a potential ligand of NOD1 in teleosts, in spotted snakehead. In addition, the temporal effect of LPS on transcriptional modulation of NOD1 and its downstream signaling molecule RIPK2 was investigated. Docking studies revealed well conserved leucine rich domains of NOD1 that could bind with LPS. Further, NACHT-ATP interactions revealed differences in ATP binding motifs within the NACHT domain in spotted snakehead compared to those reported in other fish species and mammals pointing towards species-specific nature of ATP interactions within the NACHT domain. Further, it was revealed that the ssNOD1-CARD domain interacts with the CARD domain of downstream signaling molecule ssRIPK. Interestingly, LPS treatment modulated the expression of both, ssNOD1 and ssRIPK2 in a time-dependent manner.

Characterizations of Protein Arginine Deiminase 1 as a Substrate of NTMT1: Implications of Nα-Methylation in Protein Stability and Interaction.

α-N-Methylation (Nα-methylation), catalyzed by protein N-terminal methyltransferases (NTMTs), constitutes a crucial post-translational modification involving the transfer of a methyl group from S-adenosyl-l-methionine (SAM) to the Nα-terminal amino group of substrate proteins. NTMT1/2 are known to methylate canonical Nα sequences, such as X-P-K/R. With over 300 potential human protein substrates, only a small fraction has been validated, and even less is known about the functions of Nα-methylation. This study delves into the characterizations of protein arginine deiminase 1 (PAD1) as a substrate of NTMT1. By employing biochemical and cellular assays, we demonstrated NTMT1-mediated Nα-methylation of PAD1, leading to an increase in protein half-life and the modulation of protein-protein interactions in HEK293T cells. The methylation of PAD1 appears nonessential to its enzymatic activity or cellular localization. Proteomic studies revealed differential protein interactions between unmethylated and Nα-methylated PAD1, suggesting a regulatory role for Nα-methylation in modulating PAD1's protein-protein interactions. These findings shed light on the intricate molecular mechanisms governing PAD1 function and expand our knowledge of Nα-methylation in regulating protein function.

Enhancing Built‐In Electric Field via Defect‐Mediated Interfacial Chemical Bond Construction in Chalcogenide Heterojunction for Alcohol Photooxidation Coupled with H2 Production

AbstractRationally designing nanostructures based on an adequate understanding of structure‐performance relationships is key for directional charge transfer regulation in heterojunction photocatalysts. A general strategy is developed for synthesizing bifunctional Sv‐chalcogenide/Ti3C2 Schottky junctions (Sv = sulfur vacancies, chalcogenides containing CdS, CdIn2S4, ZnIn2S4, ZnS, CuInS2) featuring a giant built‐in electric field (BIEF) via defect‐mediated heterocomponent anchorage, which consists of sulfur vacancy modulation of chalcogenides and Ti3C2 nanoparticle anchoring at defects via interfacial Metal─Oxygen (M─O) bonds. These heterojunctions have the distinctive interface structure of semicoherent phase boundaries and a directionally aligned BIEF pointing from chalcogenides to Ti3C2. The enhanced BIEF creates an asymmetrical charge distribution, which not only governs the charge migration behavior by enabling charge carrier localization and delocalized electron transport continuity but also regulates the molecular catalytic behavior by optimizing pivotal intermediate adsorption/activation (*Ar‐CH(R2)‐OH in dehydrogenation and H* in H2 evolution) in selective alcohol photooxidation coupled with H2 generation. Encouragingly, Sv‐chalcogenide/Ti3C2 exhibits unprecedented performance (up to 13.34‐fold higher efficiency than unmodulated chalcogenides) and good substrate compatibility for various alcohols. This work demonstrates the synergistic effects of surface electron density control and interfacial interaction modulation in regulating BIEFs, elucidating the substantial impact of reinforced BIEF on carrier transport properties and molecular catalytic behavior.

Biopsychosocial pathways model of early childhood appetite self-regulation: Temperament as a key to modulation of interactions among systems

The widespread discrimination against individuals with obesity often stems from a simplistic perception of obesity as a mere consequence of personal choices of overeating and insufficient physical activity. This reductionist perception fails to acknowledge the complexity of the epidemic of obesity, which extends beyond diet and exercise decisions. The concept of appetite self-regulation (ASR) has been explored as a crucial element in identifying obesogenic behavioral approaches to food. Although an extensive understanding of ASR in children is essential as an early precursor and modifiable factor influencing obesity, the prevailing view of self-regulation of eating solely as a matter of cognitive and behavioral processing tends to overlook interacting systems of influences. This narrow approach attributes obesity to the lack of voluntary self-control in food consumption while neglecting to account for the biological, psychological, and social influences implicated in the developmental processes of ASR, which may further contribute to the stigmatization of obesity. The current critical analysis provides a comprehensive developmental framework that could guide future studies with testable hypotheses, outlining pathways of interactions among biopsychosocial systems, all of which contribute to the development of ASR in early childhood. Adopting developmental perspectives allows a holistic approach to investigating ASR, which accounts for intricate interactions between biological (B), psychological (P), and social (S) factors influential in the early manifestation of ASR.

Multiple interaction solutions, parameter analysis, chaotic phenomena and modulation instability for a (3+1)-dimensional Kudryashov–Sinelshchikov equation in ideal liquid with gas bubbles

Multiple interaction solutions, parameter analysis, chaotic phenomena and modulation instability for a (3+1)-dimensional Kudryashov–Sinelshchikov equation in ideal liquid with gas bubbles

Dietary oxygenated water mitigates type 2 diabetes mellitus by modulating gut microbiota and enhancing glucose metabolism in skeletal muscle

Type 2 diabetes mellitus (T2DM) is a significant health concern resulting from dysregulation of glucose metabolism, emphasizing the need for effective dietary interventions. Emerging evidence suggests a correlation between diabetes and hypoxia, indicating that oxygenated water (ORW) may hold promise in mitigating T2DM. This study employed a multifaceted approach involving physiological, genomic, metabolomic, transcriptomic, and molecular biological analyses to investigate the effects of ORW on T2DM and its underlying mechanisms. The results demonstrated that ORW effectively ameliorated key symptoms of T2DM by improving polydipsia and polyphagia, reducing fasting blood glucose, enhancing glucose tolerance, and increasing insulin levels. Notably, the beneficial effects of ORW appeared to be mediated through modulation of gut-muscle interactions by influencing gut microbiota composition and metabolite profiles. Transcriptomic and molecular analyses revealed that ORW activated the Akt signaling pathway and upregulated key genes involved in glucose uptake and utilization in skeletal muscle, as evidenced by increased p-AKT/AKT ratio and upregulation of Irs1, Glut4, Hk2, and Pfk. Collectively, these findings demonstrate that ORW alleviates T2DM by modulating gut microbiota while enhancing glucose uptake/utilization in skeletal muscle, supporting its potential use as an effective adjuvant strategy for targeted regulation of T2DM.

Identification of sanguinarine as c-MYC transcription inhibitor through enhancing the G-quadruplex-NM23-H2 interactions

c-MYC is a proto-oncogene ubiquitously overexpressed in various cancers. The formation of G-quadruplex (G4) structures within the c-MYC promoter region can regulate its transcription by interfering with protein binding. Consequently, small molecules targeting c-MYC G4 have emerged as promising anticancer agents. Herein, we report that sanguinarine (SG) and its analogs exhibit a high affinity for c-MYC G4 and potently modulate G4-protein interactions within a natural product library. Notably, SG uniquely enhances NM23-H2 binding to c-MYC G4, both in vitro and in cellular contexts, leading to c-MYC transcriptional repression and subsequent inhibition of cancer cell growth in an NM23-H2-dependent manner. Mechanistic studies and molecular modeling suggest that SG binds to the c-MYC G4/NM23-H2 interface, acting as an orthosteric stabilizer of the DNA-protein complex and preventing c-MYC transcription. Our findings identify SG as a potent c-MYC transcription inhibitor and provide a novel strategy for developing G4-targeting anticancer therapeutics through modulation of G4-protein interactions.

Sealing the Pandora’s vase of pancreatic fistula through entrapping the digestive enzymes within a dextrorotary (D)-peptide hydrogel

A variety of therapeutic possibilities have emerged for skillfully regulating protein function or conformation through intermolecular interaction modulation to rectify abnormal biochemical reactions in diseases. Herein, a devised strategy of enzyme coordinators has been employed to alleviate postoperative pancreatic fistula (POPF), which is characterized by the leakage of digestive enzymes including trypsin, chymotrypsin, and lipase. The development of a dextrorotary (D)-peptide supramolecular gel (CP-CNDS) under this notion showcases its propensity for forming gels driven by intermolecular interaction. Upon POPF, CP-CNDS not only captures enzymes from solution into hydrogel, but also effectively entraps them within the internal gel, preventing their exchange with counterparts in the external milieu. As a result, CP-CNDS completely suppresses the activity of digestive enzymes, effectively alleviating POPF. Remarkably, rats with POPF treated with CP-CNDS not only survived but also made a recovery within a mere 3-day period, while mock-treated POPF rats had a survival rate of less than 5 days when experiencing postoperative pancreatic fistula, leak or abscess. Collectively, the reported CP-CNDS provides promising avenues for preventing and treating POPF, while exemplifying precision medicine-guided regulation of protein activity that effectively targets specific pathogenic molecules across multiple diseases.

Bioelectronic sensing platform emulating the human endocannabinoid system for assessing and modulating of cannabinoid activity

Cannabinoids are involved in physiological and neuromodulatory processes through their interactions with the human cannabinoid receptor-based endocannabinoid system. Their association with neurodegenerative diseases and brain reward pathways underscores the importance of evaluating and modulating cannabinoid activity for both understanding physiological mechanisms and developing therapeutic drugs. The use of agonists and antagonists could be strategic approaches for modulation. In this study, we introduce a bioelectronic sensor designed to monitor cannabinoid binding to receptors and assess their agonistic and antagonistic properties. We produced human cannabinoid receptor 1 (hCB1R) via an Escherichia coli expression system and incorporated it into nanodiscs (NDs). These hCB1R-NDs were then immobilized on a single-walled carbon nanotube field-effect transistor (swCNT-FET) to construct a bioelectronic sensing platform. This novel system can sensitively detect the cannabinoid ligand anandamide (AEA) at concentrations as low as 1 fM, demonstrating high selectivity and real-time response. It also successfully identified the hCB1R agonist Δ9-tetrahydrocannabinol and observed that the hCB1R antagonist rimonabant diminished the sensor signal upon AEA binding, indicating the antagonism-based modulation of ligand interaction. Consequently, our bioelectronic sensing platform holds potential for ligand detection and analysis of agonism and antagonism.

Modulation of platelet interaction with collagen by carbamylation, a non-enzymatic post-translational modification occurring during pathophysiological vascular aging

Modulation of platelet interaction with collagen by carbamylation, a non-enzymatic post-translational modification occurring during pathophysiological vascular aging