Negative Potential Research Articles

Neuroprotective efficiency of celecoxib vesicular bilosomes for the management of lipopolysaccharide-induced Alzheimer in mice employing 23 full factorial design.

The aim of this study was to develop and evaluate bilosomes loaded with Celecoxib (CXB) for the efficient treatment of Alzheimer. The thin-film hydration approach was utilized in the formulation of CXB bilosomes (CXB-BLs). The study used a 23-factorial design to investigate the impact of several formulation variables. Three separate parameters were investigated: bile salt type (X1), medication amount (X2), and lipid-bile salt ratio (X3). The dependent responses included entrapment efficiency (Y1: EE %), particle size (Y2: PS), and zeta potential (Y3: ZP). The formulation factors were statistically optimized using the Design-Expert® program. The vesicles demonstrated remarkable CXB encapsulation efficiency, ranging from 94.16 ± 1.91 to 98.38 ± 0.85%. The vesicle sizes ranged from 241.8 ± 6.74 to 352 ± 2.34nm. The produced formulations have high negative zeta potential values, indicating strong stability. Transmission electron microscopy (TEM) revealed that the optimized vesicles had a spherical form. CXB release from BLs was biphasic, with the release pattern following Higuchi's model. In vivo studies confirmed the efficiency of CXB-BLs in management of lipopolysaccharide-induced Alzheimer as CXB-BLs ameliorated cognitive dysfunction, decreased acetylcholinesterase (AChE), and inhibited neuro-inflammation and neuro-degeneration through reducing Toll-like receptor (TLR4), and Interleukin-1β (IL-1β) levels. The findings suggested that the created CXB-BLs could be a potential drug delivery strategy for Alzheimer's treatment.

Assessment of Antimicrobial and Cytotoxic Activities of Liposomes Loaded with Curcumin and Lippia origanoides Essential Oil

(1) Introduction: Curcumin and Lippia origanoides essential oils have a broad spectrum of biological activities; however, their physicochemical instability, low solubility, and high volatility limit their therapeutic use. Encapsulation in liposomes has been reported as a feasible approach to increase the physicochemical stability of active substances, protect them from interactions with the environment, modulate their release, reduce their volatility, improve their bioactivity, and reduce their toxicity. To date, there are no reports on the co-encapsulation of curcumin and Lippia origanoides essential oils in liposomes. Therefore, the objective of this work is to prepare and physiochemical characterize liposomes loaded with the mixture of these compounds and to evaluate different in vitro biological activities. (2) Methods: Liposomes were produced using the thin-layer method and physiochemical characteristics were calculated. The antimicrobial and cytotoxic activities of both encapsulated and non-encapsulated compounds were evaluated. (3) Results: Empty and loaded nanometric-sized liposomes were obtained that are monodisperse and have a negative zeta potential. They inhibited the growth of Staphylococcus aureus and did not exhibit cytotoxic activity against mammalian cells. (4) Conclusions: Encapsulation in liposomes was demonstrated to be a promising strategy for natural compounds possessing antimicrobial activity.

Ranitidine degradation in layered double hydroxide activated peroxymonosulfate system: impact of transition metal composition and reaction mechanisms.

Ranitidine, a competitive inhibitor of histamine H2 receptors, has been identified as an emerging micropollutant in water and wastewater, raising concerns about its potential impact on the environment and human health. This study aims to address this issue by developing an effective removal strategy using two types of layered double hydroxide (LDH) catalysts (i.e., CoFeLDH and CoCuLDH). Characterization results show that CoFeLDH catalyst has superior catalytic properties due to its stronger chemical bond compared to CoCuLDH. The degradation experiment shows that 100% degradation of ranitidine could be achieved within 20min using 25mg/L of CoFeLDH and 20mg/L of peroxymonosulfate (PMS). On the other hand, CoCuLDH was less effective, achieving only 70% degradation after 60min at a similar dosage. The degradation rate constant of CoFeLDH was 10 times higher than the rate constant of CoCuLDH at different pH range. Positive zeta potential of CoFeLDH made it superior over CoCuLDH regarding catalytic oxidation of PMS. The catalytic degradation mechanism shows that sulfate radicals played a more dominant role than hydroxyl radicals in the case of LDH catalysts. Also, CoFeLDH demonstrated a stronger radical pathway than CoCuLDH. XPS analysis of CoFeLDH revealed the cation percentages at different phases and proved the claim of being reusable even after 8 cycles. Overall, the findings suggest that CoFeLDH/PMS system proves to be a suitable choice for attaining high degradation efficiency and good stability in the remediation of ranitidine in wastewater.

Development of a freshness indicator packaging system using cold atmospheric plasma on LLDPE–PVA with Laponite–anthocyanin biohybrid

AbstractThis study developed a freshness indicator based on poly(vinyl alcohol) (PVA) and a biohybrid (BH) of Laponite® and anthocyanins adhered to linear low‐density polyethylene (LLDPE) using cold atmospheric plasma (CAP). LLDPE was treated with CAP for 0 to 300 s, which resulted in an increased surface energy, characterized by an important increase in its polar component up to 120 s of treatment, due to the formation of polar groups on the surface of LLDPE. No changes in mechanical properties and water vapor permeability of LLDPE were observed. LLDPE–PVA–BH films were more homogeneous if BH was added before the acidification of the film‐forming solution due to more negative zeta potential and lower particle size of BH in basic medium. Indicators made with BH were able to maintain color after 8 weeks of exposure to light, while those made with anthocyanin extract had fully degraded after 3 weeks. The freshness indicator's color changed from purple to blue and finally to green when exposed to ammonia hydroxide (30% NH3) and from purple to blue when exposed to a simulant liquid of spoiled meat (0.03% NH3). Similar color variance was observed when the indicator was applied to monitor shrimp freshness, changing from purple to blue when the shrimp pH reached pH 7.6. Thus, bilayer films of LLDPE–PVA and natural BH produced using CAP have potential food packaging applications. © 2024 Society of Chemical Industry.

Late Positive Potential Elicited by Monetary Reward Feedback Predicts Changes of Disordered Eating From Age11 to Age 12 in Community-Dwelling Girls.

Early adolescence is marked by elevated psychopathology, including disrupted eating attitudes and behaviors. Reward processing is an identified mechanism in portending eating pathology, that is, aberrant reward responsivity may contribute to disrupted reward-seeking behaviors (e.g., food consuming). This literature has focused on adults or mid-to-late adolescents, with little work done on early adolescence. We examined the linkages between reward feedback processing, indexed by event-related potentials (ERPs), and changes of emerging disordered eating in community-dwelling early adolescents. At T1, 115 youths (66 girls, mean/SD age = 11.00/1.16 years) completed an EEG monetary reward Doors task. Youths completed the Eating Disorder Examination-Questionnaire Short at T1 and ~6 months (T2) and ~12 months (T3) after T1. In the ERP data, we isolated a reward positivity (RewP) and a late positive potential (LPP) via principal component analysis. We applied multilevel modeling to examine whether baseline ERPs interacted with Time in predicting disordered eating and whether these interactions varied by sex. We found a significant Time × LPP interaction in girls but not boys. Among girls, only those with a smaller LPP toward the losses (versus wins), which might reflect suboptimal evaluation and regulatory processes in undesired situations, showed increases in disordered eating from T1 to T3. We provided preliminary yet novel evidence concerning the prospective associations between reward processing and changes of disordered eating in early adolescents. Future studies along this line will be critical for understanding the early mechanisms of eating pathology, identifying youths at risk, and developing prevention strategies.

Complexes of Zinc-Coordinated Heteroaromatic N-Oxides with Pyrene: Lewis Acid Effects on the Multicenter Donor–Acceptor Bonding

4-Nitroquinoline-N-oxide (NQO) and 4-nitropyridine-N-oxide (NPO) are important precursors for the synthesis of substituted heterocycles while NQO is a popular model mutagen and carcinogen broadly used in cancer research; intermolecular interactions are critical for their reactions or functioning in vivo. Herein, the effects of the coordination of N-oxide’s oxygen atom to Lewis acids on multicenter donor–acceptor bonding were explored via a combination of experimental and computational studies of the complexes of NQO and NPO with a typical π-electron donor, pyrene. Coordination with ZnCl2 increased the positive electrostatic potentials on the surfaces of these π-acceptors and lowered the energy of their LUMO. Analogous effects were observed upon the protonation of the N-oxides’ oxygen or bonding with boron trifluoride. The interaction of ZnCl2, NPO, or NQO and pyrene resulted in the formation of dark co-crystals comprising π-stacked Zn-coordinated N-oxides and pyrene similar to that found with protonated or (reported earlier) BF3-bonded N-oxides. Computational studies indicated that the coordination of N-oxides to zinc(II), BF3, or protonation led to the strengthening of the multicenter bonding of the nitro-heterocycle with pyrene, and this effect was related both to the increased electrostatic attraction and molecular–orbital interactions in their complexes.

Chitosan Coating as a Strategy to Increase Postemergent Herbicidal Efficiency and Alter the Interaction of Nanoatrazine with Bidens pilosa Plants.

The atrazine nanodelivery system, composed of poly(ε-caprolactone) (PCL+ATZ) nanocapsules (NCs), has demonstrated efficient delivery of the active ingredient to target plants in previous studies, leading to greater herbicide effectiveness than conventional formulations. Established nanosystems can be enhanced or modified to generate new biological activity patterns. Therefore, this study aimed to evaluate the effect of chitosan coating of PCL+ATZ NCs on herbicidal activity and interaction mechanisms with Bidens pilosa plants. Chitosan-coated NCs (PCL/CS+ATZ) were synthesized and characterized for size, zeta potential, polydispersity, and encapsulation efficiency. Herbicidal efficiency was assessed in postemergence greenhouse trials, comparing the effects of PCL/CS+ATZ NCs (coated), PCL+ATZ NCs (uncoated), and conventional atrazine (ATZ) on photosystem II (PSII) activity and weed control. Using a hydroponic system, we evaluated the root absorption and shoot translocation of fluorescently labeled NCs. PCL/CS+ATZ presented a positive zeta potential (25 mV), a size of 200 nm, and an efficiency of atrazine encapsulation higher than 90%. The postemergent herbicidal activity assay showed an efficiency gain of PSII activity inhibition of up to 58% compared to ATZ and PCL+ATZ at 96 h postapplication. The evaluation of weed control 14 days after application ratified the positive effect of chitosan coating on herbicidal activity, as the application of PCL/CS+ATZ at 1000 g of a.i. ha-1 resulted in better control than ATZ at 2000 g of a.i. ha-1 and PCL+ATZ at 1000 g of a.i. ha-1. In the hydroponic experiment, chitosan-coated NCs labeled with a fluorescent probe accumulated in the root cortex, with a small quantity reaching the vascular cylinder and leaves up to 72 h after exposure. This behavior resulted in lower leaf atrazine levels and PSII inhibition than ATZ. In summary, chitosan coating of nanoatrazine improved the herbicidal activity against B. pilosa plants when applied to the leaves but negatively affected the root-to-shoot translocation of the herbicide. This study opens avenues for further investigations to improve and modify established nanosystems, paving the way for developing novel biological activity patterns.

Understanding the Decamethylferrocene FeIII/IV Oxidation Process in Tris(pentafluoroethyl)trifluorophosphate-Containing Ionic Liquids at Glassy Carbon and Boron-Doped Diamond Electrodes.

Under voltammetric conditions, the neutral decamethylferrocene ([Me10Fc]) to cationic ([Me10Fc]+) FeII/III process is a well-known reversible outer-sphere reaction. A companion cationic [Me10Fc]+ to dicationic [Me10Fc]2+ FeIII/IV process has been reported under direct current (DC) cyclic voltammetric conditions at highly positive potentials in liquid SO2 at low temperatures and in a 1.5:1.0 AlCl3/1-butylpyridinium chloride melt. This study demonstrates that in room-temperature ionic liquids containing the hard to oxidize and hydrophobic tris(pentafluoroethyl)trifluorophosphate anion, the [Me10Fc]+/2+ process can be detected as a quasi-reversible reaction at glassy carbon (GC) and boron-doped diamond (BDD) electrodes. Large amplitude Fourier-transformed alternating current (FT-AC) voltammetry minimizes background current contributions occurring at potentials similar to those of the FeIII/IV process in the second and higher-order harmonics. This enables a straightforward determination of the thermodynamics and kinetics for both the FeII/III and FeIII/IV processes. Unlike the ideal outer-sphere FeII/III process, the parameters of the FeIII/IV process may be impacted by ion-interaction effects. For the faster FeII/III process, heterogeneous rate constants are approximately 10 times smaller at BDD than those at GC electrodes. This electrode dependence is less pronounced for the slower FeIII/IV process. The slower BDD kinetics may be attributed in part to a density of states lower than that at GC.

Multi-Species Biofilm Interactions and Their Impact on the Biocorrosion of Copper-Coated CoCr Alloys in Dental Application

Biocorrosion of materials used in dental restorations is a complex process involving various bacterial species that coexist as biofilms. Since copper possesses excellent antibacterial properties, it could help minimize this problem. The aim of this study is to assess the antibiofilm characteristics and corrosion resistance of CoCr and copper-coated CoCr alloys in a multispecies biofilm model. CoCr alloys and CoCr coated with copper (CoCr/Cu) using Physical Vapor Deposition (PVD) were investigated. The samples were incubated in media with and without a multispecies biofilm for 24 h and for 15 days. Potentiodynamic Polarization and Electrochemical Impedance Spectroscopy (EIS) were used to assess the corrosion behavior of the samples. Scanning Electron Microscopy (SEM) was utilized to observe the growth of multispecies biofilms and the type of corrosion. The Mann–Whitney U test was employed to examine corrosion results, with significant differences defined as p < 0.05. CoCr/Cu alloys demonstrated superior corrosion resistance at 24 h and 15 days in the presence of biofilm compared to those without coating. No differences were observed in multispecies biofilm formation at 24 h. The study demonstrates that copper-coated CoCr alloys (CoCr/Cu) exhibit a more positive corrosion potential (Ecorr) compared to uncoated CoCr alloys, both in the presence and absence of multispecies biofilm (BP) at 24 h and 15 days. After 15 days, the potential of CoCr/Cu with BP was −0.144 V, compared to −0.252 V for uncoated CoCr. These significant differences in Ecorr values underscore the protective effect of copper against corrosion in multispecies biofilm environments.

Chiral Effect on the Electrochemistry of Magnetic Ferrite Colloidal Nanocrystal Assembly Modified by Amino Acids.

Chirality on the molecular or nanometer scale is particularly significant in chemistry, materials science, and biomedicine. Chiral electrochemical reactions on solid surfaces are currently a hot research topic. Herein, a chiral solid surface is constructed in aqueous solutions by mixing chiral molecules, d- and l-glutamic, with γ-Fe2O3 and Fe3O4 nanoparticles (NPs) and MnFe2O4 colloidal nanocrystal assembly (CNA). Cyclic voltammetry and differential pulse voltammetry measurements are conducted in a phosphate buffer solution (PBS) containing ascorbic acid (AA) or isoascorbic acid (IAA), and a chiral effect appears on the electroreduction of ferric ions of amino acid-modified magnetic samples. A negative or positive potential shift is observed, respectively, for magnetic structures modified by l- and d-glutamic acid in aqueous AA electrolyte, while the opposite is observed for these samples in IAA electrolyte. The reduction peak current increases by 0.8-1.2 times for the electrodes modified with l- and d-glutamate molecules, improving the electron transport efficiency. The chiral effect is absent when the electrolytes contain achiral uric acid or dopamine, or even chiral l-/d-/ld-tartaric acid. The chiral recognition between d-/l-glutamic acid and AA/IAA at the electrochemical interface is suggested to be related to their spinal configurations. These observations will be helpful for the rational design of inorganic functional chiral micro/nanostructures.

Chiral Effect on the Electrochemistry of Magnetic Ferrite Colloidal Nanocrystal Assembly Modified by Amino Acids.

Chirality on the molecular or nanometer scale is particularly significant in chemistry, materials science, and biomedicine. Chiral electrochemical reactions on solid surfaces are currently a hot research topic. Herein, a chiral solid surface is constructed in aqueous solutions by mixing chiral molecules, d- and l-glutamic, with γ-Fe2O3 and Fe3O4 nanoparticles (NPs) and MnFe2O4 colloidal nanocrystal assembly (CNA). Cyclic voltammetry and differential pulse voltammetry measurements are conducted in a phosphate buffer solution (PBS) containing ascorbic acid (AA) or isoascorbic acid (IAA), and a chiral effect appears on the electroreduction of ferric ions of amino acid-modified magnetic samples. A negative or positive potential shift is observed, respectively, for magnetic structures modified by l- and d-glutamic acid in aqueous AA electrolyte, while the opposite is observed for these samples in IAA electrolyte. The reduction peak current increases by 0.8-1.2 times for the electrodes modified with l- and d-glutamate molecules, improving the electron transport efficiency. The chiral effect is absent when the electrolytes contain achiral uric acid or dopamine, or even chiral l-/d-/ld-tartaric acid. The chiral recognition between d-/l-glutamic acid and AA/IAA at the electrochemical interface is suggested to be related to their spinal configurations. These observations will be helpful for the rational design of inorganic functional chiral micro/nanostructures.

Effect of Heat Treatment and Hot Isostatic Pressing on the Corrosion Behavior of Ti6Al4 V Parts Produced by Electron Beam Melting Additive Manufacturing Technology.

In this study, we investigated the effect of heat treatment (HT) and hot isostatic press (HIP) on the corrosion behavior of Ti6Al4 V, manufactured by electron beam melting (EBM) additive manufacturing. The preliminary results showed that the thermal process makes the columnar structure more pronounced and the α-lathe coarser compared to EBM. The β phase disappeared with the aging treatment and when increasing the HIP temperature treatment. According the open circuit potential (E ocp) behavior of samples, the HIP3 sample had performed more positive corrosion potential than rivals after 2 h of immersion probably due to equiaxed grain with coarser α-late and the absence of the β phase. In adverse, inferior corrosion behavior was observed for HIP1 because of a higher quantity of the β phase causing probably galvanic corrosion. The HIP process leads to a lower corrosion potential than EBM. At least one protective oxide layer formation was observed for all samples at the anodic branch, and the current density was lower for the HT3 sample. The microstructure analysis revealed the presence of the β-phase in the form of needle-like for the HT1 sample and HIP1 in the corroded area. Furthermore, the EDS line analysis showed the presence of aluminum with oxygen at the edge of the corrosion area for HIP1 suggesting aluminum plays a barrier against degradation. On the other hand, the HT1 showed higher impedance resistance due to the coarser α-lathe microstructure and well-defined β phase.

A mechanical nano sensor based on magnetic-mediated sensitization for 5-HT detection

The real-time detection of neurotransmitters had attracted more attention due to the potential to provide vital information for pathology research, disease diagnosis, and clinical efficacy evaluation. Here, a magnetic-mediated nano sensor was developed to improve sensitivity for detection of serotonin (5-HT). The PDMS membrane doped with magnetic particles serves as a conversion element, enhancing the deformation of the thin film caused by surface stress under the action of a magnetic field and amplifying the resistance response signal of the nano sensor. The 5-HT detection associated with neurotransmitter diseases serve as a proof of concept revealing the magnetic sensitization. The detection limit of the 5-HT was decreased to 3.21 nM in the linear range of 5–500 nM, which was lower than that of the nano sensor without magnetic field. The clinical 5-HT samples were also been accurately detected, indicating a positive application potential of the as-prepared magnetic-mediated nano sensor. All these results reveal the high sensitivity and practicality of the as-prepared magnetic-mediated nano sensor and provide a new method for neurotransmitter diseases diagnosis.

Emotion regulation flexibility: EEG/EMG predictors and consequences of switching between reappraisal and distraction strategies.

Flexible use of emotion regulation (ER) strategies is central to mental health. To advance our understanding of what drives adaptive strategy-switching decisions, in this preregistered study, we used event-related potentials (late positive potential, LPP and stimulus preceding negativity, SPN) and facial electromyography (EMG corrugator activity) to test the antecedents and consequences of switching to an alternative ER strategy. Participants (N = 63, Mage = 24.8 years, all female) passively watched and then implemented an instructed ER strategy (reappraisal or distraction) in response to high-intensity negative pictures that were either easy or difficult to reinterpret (high or low reappraisal affordance, respectively). Next, they decided to "switch from" or "maintain" the instructed strategy and subsequently implemented the chosen strategy. Reappraisal affordance manipulations successfully induced switching. Regarding antecedents, switching was predicted by the reduced ER efficacy of the current strategy (corrugator, but not LPP). Switching to distraction was additionally predicted by increased responses to the stimulus during passive viewing (corrugator and LPP) and increased anticipatory effort in implementing reappraisal (SPN). Concerning consequences, switching to distraction improved, whereas switching to reappraisal impaired post-choice ER effects (LPP). However, starting with reappraisal was overall more effective than starting with distraction, irrespective of the subsequent decision (corrugator). Our results suggest that switching between ER strategies occurs in accordance with situational demands (stimulus affordances) and is predicted by reduced peripheral physiological ER efficacy. However, only switching to distraction leads to improved regulatory effects. These insights provide neurocognitively grounded starting points for developing interventions targeting ER flexibility.

Intimate relationships regulate female brain activity in a competitive context: evidence from EEG and functional connectivity analysis.

Competition is common in life, and intimate relationships are essential. Understanding how intimate relationships impact an individual's competitive process is crucial. This study explored the impact of competitor gender on female competition using electroencephalography analysis. The results revealed that females exhibited a smaller median of the absolute value of reaction time difference (DRT) between their partners and their competitors when their partners were absent compared to when their partners were present. Additionally, females showed greater average amplitudes of N2 posterior contralateral component (N2pc) and Late Positive Potential (LPP), increased activation of the alpha frequency band, and enhanced theta frequency band functional connectivity between the central parietal lobe and occipital lobe. Furthermore, when competing with individuals of the same gender as opposed to individuals of the opposite gender, females exhibited greater average amplitudes of percentage of wins and N2pc. A significant negative correlation was noted between the DRT and the average wave amplitudes of N2pc and LPP. These findings suggest that females are more engaged in competitive tasks when partners are not present and have improved decision-making when competing with same-gender individuals. This study provides evidence for the influence of lovers on female competition, helping females adapt to social competition and promoting healthy relationships.

A Pilot Study on the Efficacy of an App-Based Rehabilitation Counselling Program after Total Knee Arthroplasty.

The aim of this study was to determine the effects of a novel app-based rehabilitation counselling program in patients recovering from total knee arthroplasty. In the app-based rehabilitation counselling program, a counselor provides one-on-one rehabilitation exercises and management-focused psychological counselling after total knee arthroplasty (TKA). This study included 42 patients, who were divided into three groups of 14 patients each: Group A, whose rehabilitation training was based on a guideline leaflet; Group B, whose rehabilitation was based on the app-based rehabilitation counselling program; and Group C, whose rehabilitation training was based on continuous passive motion combined with the app-based rehabilitation counselling program. To determine the effects of rehabilitation, the isokinetic knee muscle strength and knee joint range of motion were measured in addition to knee function tests such as the Western Ontario and McMaster Universities Osteoarthritis Index (WOMAC) and the visual analogue scale (VAS) for pain at two and three months after rehabilitation. The comparison of the means of the three groups was analyzed using one-way analysis of variance (ANOVA), with Group C showing significant variance in isokinetic knee muscle strength (p < 0.05), passive ROM (p < 0.01), and WOMAC (p < 0.05) after three months. As a result, this study confirmed the positive potential of the app-based rehabilitation counselling program.

Electrochemical Evaluation of Penta‐Coordinated Fe Phthalocyanine During the Oxygen Reduction Reaction in Various Acidic Solutions

AbstractIron phthalocyanine (FePc) was penta‐coordinated with pyridine ligand (Py) grafted on carbon nanotube (CNT), to form (FePc‐Py‐CNT). The complex was studied as a catalyst for the oxygen reduction reaction ORR in seven different supporting electrolytes: OH− (0.1 M), OH− (1 M), NO3− (1 M), HSO4− (1 M), ClO4− (1 M), Br− (1 M), Cl− (1 M), to unveil anion‐poisoning effects and mechanism. Through cyclic voltammetry and polarization curves in N2 and O2 saturated atmospheres, thermodynamic and kinetic data were acquired. In acid media, the formal potential Fe(III)/(II) (E0’Fe(III)/(II)) of the complex is biased to more negative potentials by the anion presence. Similar effects were observed for the onset potential (Eonset) during polarization curves for the ORR. When the ORR was performed in the presence of either ClO4−, or HSO4−, anions, Tafel analysis showed different values depending if were derived from the low or from the high overpotential regions, revealing an inner‐sphere electron transfer mechanism (ISET). The Tafel values derived from measurements in the presence of Cl− and Br− anions do not change when extracted at low or at high overpotentials evidencing an outer‐sphere reaction mechanism (OSET). Gibbs free energies were derived from poisoning tests confirming the ISET and OSET mechanisms. The poisoning effect is responsible for the immediate loss of performance for these catalysts during the ORR in acidic media.

Crystal-Defect-Induced Longer Lifetime of Excited States in a Metal-Organic Framework Photocatalyst to Enhance Visible-Light-Mediated CO2 Reduction.

We report the structural defects in Zr-metal-organic framework (MOFs) for achieving highly efficient CO2 reduction under visible light irradiation. A series of defective Zr-MOF-X (X = 160, 240, 320, or 400) are synthesized by acid-regulated defect engineering. Compared to pristine defect-free Zr-MOF (NNU-28), N2 uptake increases for Zr-MOF-X synthesized with the HAc modulator, producing a larger pore space and Brunauer-Emmett-Teller surface area. The pore size distribution demonstrates that defective Zr-MOF-X exhibits mesoporous structures. Electrochemistry tests show that defective Zr-MOF-X possesses a more negative reduction potential and a higher photocurrent responsive signal than that of pristine NNU-28. Consequently, the defective samples exhibit a significantly higher efficiency in the photoreduction of CO2 to formate. Transient absorption spectroscopies manifest that structural defects modulate the excited-state behivior of Zr-MOF-X and improve the photogenerated charge separation of Zr-MOF-X. Furthermore, electron paramagnetic resonance and in-suit X-ray photoelectron spectroscopy provide additional evidence of the high photocatalytic performance exhibited by defective Zr-MOF-X. Results demonstrate that structural defects in Zr-MOF-X also improve the charge transfer, producing abundant Zr(III) catalytically active sites, exhibiting a slower decay process than defect-free Zr-MOF. The long-lifetime Zr(III) species in defective Zr-MOF-X are fully exposed to a high-concentration CO2 atmosphere, thereby enhancing the photocatalytic efficiency of CO2 reduction.

First-principles calculation of monolayer PdSe2 with Se and Pd vacancy and its effect on quantum capacitance

Abstract The emergence of 2-D materials such as graphene has caught the attention of the scientific community. 2-D materials have a higher surface area per unit mass, which is ideal for electrodes. Another popular material among researchers is the monolayer palladium diselenide or PdSe2, a semiconductor with a tunable bandgap energy. Since there are fewer states in the fermi level of PdSe2, the quantization effect is more prevalent, hence, it would most likely draw its capacitance from its electronic configuration. In this study, the electronic properties such as band structure, density of states, and quantum capacitance of pristine monolayer PdSe2, PdSe2 with Se, and Pd vacancy were calculated based on density functional theory via Quantum Espresso. The formation energies of all systems were energetically favourable. The system with Se vacancy has the highest formation energy with a value of -3.47 eV. The density of states of all systems were observed to have a local minima at the fermi level. More occupiable states around the valence band were observed for the systems with vacancy. Bader charge analysis showed a notable decrease of charge in Se atoms near the Pd vacancy, while the Pd atoms in the Se vacated system showed stronger charge transfer between Pd and another Se atom. The quantum capacitance and surface charge values were calculated using the density of states. Higher surface charge values at the negative voltage were observed for the systems with induced vacancies. Based on the results, the systems with vacancies have improved the quantum capacitance and surface charge at the negative potential.

Revitalizing CO2 photoreduction: Fine-tuning electronic synergy in ultrathin g-C3N4 with amorphous (CoFeNiMnCu)S2 high-entropy sulfide nanoparticles for enhanced sustainability

Sustainability is a key issue in developing stable and efficient catalysts for solar-catalyzed CO2 conversion. The concept of structural stabilization by quenching the Gibbs free energy, which is achieved by increasing the configurational entropy level of the system, introduced high-entropy materials. However, because alloying immiscible multimetallic atoms into a unit system is still an arduous process, the potential of high-entropy materials has not yet been fully exploited. Surprisingly, although metal sulfide photocatalysts have an enviable reputation for CO2 photoreduction (CO2-PR) owing to their optical/electronic merits and more negative redox potential than other materials, the capability of high-entropy metal sulfides has been completely disregarded. Herein, an adaptable, self-templating metal alkoxide appropriately addresses the immiscibility of metallic constituents by the well-blended metal ions with polyalcohol in the metal glycerate. Consequently, (CoFeNiMnCu)S2 high-entropy metal sulfide nanoparticles (HEMS-Nps) were grown in situ on crossed ultrathin g-C3N4 (UCN) monolayers during the sulfidation of the metal glycerate. The as-synthesized HEMS-Np has a crystalline–amorphous structure, which is conducive to the acceleration of charge transfer to/from reaction sites, and a convincing orientation for CO2 adsorption. These features are combined with synergistic electronic multimetallic interactions, facilitating a heterogeneous valence electron distribution and atomic disorder. The CO2-PR power of the (CoFeNiMnCu)S2@UCN nanostructure was noticeable in realizing added-value products in both the liquid–solid (1063 µmol/g h of syngas and 250 µmol/g h of methane) and gas–solid phases (1883 µmol/cm2 h of syngas and 321 µmol/cm2 h of methane). To prove its utility, long-term and corresponding time-equivalent cycling experiments were conducted, demonstrating a highly stable system that endured for a long time. Overall, this approach simultaneously exploits the advantages of sulfide-based materials and high-entropy materials in stable structures to generate sustainable CO2-PR materials.