Peak Potential Research Articles

Unlocking Superior Hydrogen Oxidation and CO Poisoning Resistance on Pt Enabled by Tungsten Nitride-Mediated Electronic Modulation.

Enhancing the activity and CO poisoning resistance of Pt-based catalysts for the anodic hydrogen oxidation reaction (HOR) poses a significant challenge in the development of proton exchange membrane fuel cells. Herein, we leverage theoretical calculations to demonstrate that tungsten nitride (WN) can intricately modulate the electronic structure of Pt. This modulation optimizes the hydrogen adsorption, significantly boosting HOR activity, and simultaneously weakens the CO adsorption, markedly improving resistance to CO poisoning. Through prescreening with rational design, we synthesized an efficient catalyst comprising a minimal Pt content (only 1.4 wt %) supported on the small-sized WN/reduced graphite oxide (Pt@WN/rGO). As anticipated, this catalyst showcases a remarkable acidic HOR mass activity of 3060 A gPt-1, which is approximately 11.8 times greater than that of the commercial 20 wt % Pt/C catalyst. Impressively, it maintains high activity with 98.2% retention even in the presence of 1000 ppm of CO, indicating exceptional poison resistance. Operando synchrotron radiation analyses reveal that WN harmonizes the electron state of Pt during electrochemical reactions, optimizing hydrogen adsorption/desorption dynamics. This leads to a lower peak potential of CO stripping on Pt@WN/rGO compared to that on Pt/rGO, suggesting that WN mitigates competitive CO adsorption and enhances the availability of hydrogen adsorption sites on Pt. The synergistic effect significantly accelerates HOR activity and increases antipoisoning efficacy. The assembled PEMFC demonstrates substantial tolerance to CO concentration from 10 to 1000 ppm in the H2/CO mixture.

Ambient Air-Synthesized CsPbBr3 Nanocrystals Coupled with TiO2 Film as an Efficient Hybrid Photoanode for Photoelectrochemical Methanol-to-Formaldehyde Conversion.

Due to its exceptional optoelectronic properties in the visible spectrum, cesium lead bromide (CsPbBr3) perovskite has attracted considerable attention in solar-driven organic transformations via photoelectrochemical (PEC) cells. However, the performance of the devices is adversely affected by electron-hole recombination occurring between a transparent conductive substrate, such as fluorine-doped tin dioxide (FTO), and a perovskite layer. Herein, to mitigate this issue, a compact layer of titanium dioxide (TiO2) was employed as both an electron transport layer and a hole blocking layer to diminish charge recombination while facilitating electron transfer in such perovskite material. At the oxidation peak potential of 0.70 V vs Ag/AgNO3, a hybrid photoanode of CsPbBr3/TiO2/FTO exhibited a significant increase in photocurrent density, from 15 to 41 μA/cm2, compared to a configuration without a TiO2 layer. Furthermore, the introduction of methanol as a hole scavenger in the PEC system using the hybrid photoanode facilitated the separation of electron-hole pairs, which led to an enhanced photocurrent density of 60 μA/cm2 and promoted the production of formaldehyde. High-performance liquid chromatography (HPLC) confirmed the generation of formaldehyde at a concentration of 26.69 μM with a Faradaic efficiency of 92% under an applied potential of 0.50 V vs Ag/AgNO3 for 60 min of PEC reaction. In addition to the enhanced PEC performance achieved from this hybrid photoanode, CsPbBr3 nanocrystals (NCs) in this work were synthesized by the modified one-pot method under ambient air, where highly uniform and high-purity NCs were obtained. This work signifies the groundbreaking exploration of CsPbBr3 NCs with TiO2 as a photoelectrode material in the organic-based PEC cells, which efficiently improved the interfacial charge transfer within the photoanode for the conversion of methanol to formaldehyde, marking a significant advancement in the field.

Thrombin generation assay in COVID-19 patients shows a hypocoagulable pattern

Patients with COVID-19 often exhibit coagulopathy, which can significantly impact prognosis. Therefore, investigating coagulation in this context is clinically relevant. The thrombin generation assay (TGA) provides comprehensive data on individual clotting patterns. In our study, we utilized a calibrated automated thrombogram to globally assess coagulation in COVID-19 patients. The study included 67 COVID-19 patients (40 hospitalized in the medical ward and 27 in intensive care units) and 45 blood donors for comparison. Our analysis revealed significant differences in TGA parameters (lag time, time-to-peak, thrombin peak, and endogenous thrombin potential) between patients and blood donors, suggesting a hypocoagulable state in the former. Specifically, COVID-19 patients exhibited prolonged lag time and time-to-peak values, as well as lower thrombin peak and endogenous thrombin potential compared to blood donors (Mann-Whitney test: p<0.05); notably, no significant differences in thrombin generation were observed based on the clinical setting. These findings suggest a reduced capacity for thrombin generation, indicating a consumptive coagulopathy in COVID-19 patients and that in this context, thrombosis is primarily attributable to localized effects in the lungs, platelet activation, and/or prothrombotic endothelial dysfunction. The thrombin generation assay is instrumental in defining coagulation patterns in COVID-19 and may also be applicable to other infectious diseases.

Cholesteryl Phenolipids as Potential Biomembrane Antioxidants

The lipophilization of polyphenols (phenolipids) may increase their affinity for membranes, leading to better antioxidant protection. Cholesteryl esters of caffeic, dihydrocaffeic, homoprotocatechuic and protocatechuic acids were synthetized in a one-step procedure with good to excellent yields of ~50–95%. After evaluation of their radical scavenging capacity by the DPPH method and establishing the anodic peak potential by cyclic voltammetry, their antioxidant capacity against AAPH-induced oxidative stress in soybean PC liposomes was determined. Their interaction with the liposomal membrane was studied with the aid of three fluorescence probes located at different depths in the membrane. The cholesteryl esters showed a better or similar radical scavenging capacity to that of α-tocopherol and a lower anodic peak potential than the corresponding parental phenolic acids. Cholesteryl esters were able to protect liposomes to a similar or greater extent than α-tocopherol. However, despite their antiradical capacity and being able to penetrate and orientate in the membrane in a parallel position to phospholipids, the antioxidant efficiency of cholesteryl esters was deeply dependent on the phenolipid polyphenolic moiety structure. When incorporated during liposome preparation, cholesteryl protocatechuate and caffeate showed more than double the activity of α-tocopherol. Thus, cholesteryl phenolipids may protect biomembranes against oxidative stress to a greater extent than α-tocopherol.

Cobalt vanadate intertwined in carboxylated multiple-walled carbon nanotubes for simultaneous electrochemical detection of ascorbic acid, dopamine and uric acid

Low-cost transition metal vanadate-based electrochemical sensors have attracted a lot of attention recently. A cobalt vanadate and carboxylated multi-walled carbon nanotube composite (CoV/MWCNTs-COOH) was prepared by an ultrasonic-assisted assembly method. The uniform and dense MWCNTs-COOH attached to the surface of CoV not only combines the large surface area and superior conductivity of MWCNTs-COOH with the excellent electrochemical activity of CoV, but also enhances the redox reaction between CoV/MWCNTs-COOH composite and the analyte through synergistic effect of hydrogen bonding and electrostatic interaction. The electrochemical behaviors of CoV/MWCNTs-COOH composite modified glassy carbon electrode (CoV/MWCNTs-COOH/GCE) were investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV). The simultaneous electrochemical sensing of ascorbic acid (AA), dopamine (DA) and uric acid (UA) on CoV/MWCNTs-COOH/GCE possesses good peak current signals with well-defined peak potentials. The linear ranges of AA, DA, and UA at CoV/MWCNTs-COOH/GCE are 1.0–100.0 μM, and the limits of detection (LODs; S/N = 3) are 0.4 μM, 0.03 μM, and 0.1 μM, respectively. The practicality of the designed sensor was further confirmed by the good recoveries obtained in the simultaneous measurement of actual samples including fetal bovine serum, human serum, urine, and Vitamin C tablets. Overall, the developed electrochemical sensor shows potential therapeutic applications for simultaneous determination of AA, DA and UA in biological fluids.

Oxidation Potential of 2,6-Dimethyl-1,4-dihydropyridine Derivatives Estimated by Structure Descriptors

Linear relationships, expressing the electrochemical properties of molecules as functions of structure, give insight into the associated electrochemical process and are a tool for prediction. Many biological activities rely on water-based dissociation, making electrochemical properties a bridge between structure and activity. Motivated by a previous study, a replica is made here on a different dataset in order to validate/invalidate the previously reported results. There are several methods for obtaining structure-based descriptors. Some of the methods have been devised to account for molecular topology, some to account for molecular geometry, and others to account for both. Two methods are involved here to derive structure-based descriptors and further obtain structure–property relationships (FMPI and ChPE). In order to express structure descriptors, both FMPI and ChPE express first the topology of the molecule, using the heavy atoms identity matrix and the heavy atoms adjacency matrix, both square symmetric matrices in the belief that symmetry is one major factor of molecular stability. A set of 2,6-dimethyl-1,4-dihydropyridine derivatives with oxidation peak potentials and coulometrically determined number of electrons experimental data is subjected to the search for structure–activity relationships. Even if the 2,6-dimethyl-1,4-dihydropyridine is a symmetric compound (of Cs point group), their derivatives are generally not symmetric (9 out of 24 are asymmetric). The dataset is subjected to descriptive and inferential statistics in order to filter out the most relevant structure–activity relationship. The geometry is built using three levels of theory (one from molecular mechanics and two others from density functionals, of which one accounts for the interaction with water as solvent). One challenge of picking one out of two reported measured values is dealt with by calculating the likelihood associated with the two choices. Relevant structure–activity models are extracted and discussed. The use of in vivo (in water, SM8 model) models in geometry optimization (from MMFF94 and B3LYP and to M06 + Water SM8) results in a precision gain, but this is, in most of the cases, not statistically significant, and this can be considered a negative result.

Ab Initio Kinetics of Electrochemical Reactions Using the Computational Fc0/Fc+ Electrode.

The current state-of-the-art electron-transfer modeling primarily focuses on the kinetics of charge transfer between an electroactive species and an inert electrode. Experimental studies have revealed that the existing Butler-Volmer model fails to satisfactorily replicate experimental voltammetry results for both solution-based and surface-bound redox couples. Consequently, experimentalists lack an accurate tool for predicting electron-transfer kinetics. In response to this challenge, we developed a density functional theory-based approach for accurately predicting current peak potentials by using the Marcus-Hush model. Through extensive cyclic voltammetry simulations, we conducted a thorough exploration that offers valuable insights for conducting well-informed studies in the field of electrochemistry.

Nanophase-separated ternary PdAgCu nanotubes with rich interfaces for enhanced formic acid oxidation reaction

Herein, a facile strategy for the preparation of PdAgCu ternary nanotubes (NTs) is introduced by using Cu nanowires (NWs) as sacrificial templates along with an acid-leaching treatment. Since the phase separation between Ag and Cu, the obtained PdAgCu NTs is made up of various nanosphases including pure Ag, Cu, bimetallic PdCu and PdAg nanoalloys, instead of PdAgCu trimetallic nanoalloys. By adjusting the types of solvents during synthesis, the surface morphology of PdAgCu NTs can be tuned from smooth (S-PdAgCu NTs) to rough (R-PdAgCu NTs). Both S-PdAgCu NTs and R-PdAgCu NTs exhibit excellent electrocatalytic performances for formic acid oxidation reaction (FAOR). Remarkably, the mass activity of S-PdAgCu NTs for FAOR can reach up to 4307 mA mgPd-1 at peak potential, which is 8.5 times higher than that of commercial Pd (506 mA mgPd-1). The impressively enhanced activity should be ascribed to the synergistic effect of Pd with Cu or Ag and the multi-phase interface engineering, which is resulting from the tight position relationships among different monometallic or bimetallic alloy nanophases.

Comprehensive investigation of Zinc and Tin-based metal oxides for advanced electrochemical detection of organophosphate pesticides

Different metal oxides (MOs) nanomaterials of ZnO, SnO2, and nanocomposites ZnO:SnO2 with various ratios of (1:9), (2:8), and (3:7) were prepared and coated on GCE. All MOs were tested as sensing materials for organophosphate pesticide detection. Among all MOs, ZnO:SnO2 (1:9) coated GCE increases redox peak current at different buffer solutions with varying pH compared to bare and coated GCE. Among different pH, ZnO:SnO2 (1:9) coated GCE significantly enhanced the redox peak at pH 6.2, emphasizing optimal electrochemical conditions for pesticides. Moreover, among these pH values, ZnO:SnO2 (1:9) coated GCE significantly enhanced the redox peak at pH 6.2, emphasizing optimal electrochemical conditions for the given pesticides. The morphological, elemental compositions and structural characterization of different MO nanomaterials were examined using field-emission scanning electron microscopy (FESEM), energy dispersive X-ray spectrum (EDX), and X-ray diffraction (XRD), which was further carried out to evaluate the electrocatalytic activity towards DiZn sensing. Furthermore, the electrochemical behavior of the ZnO:SnO2 (1:9) coated GCE was evaluated using cyclic voltammetry (CV) with 0.5 mL (5 mM) potassium ferrocyanide, resulting a pronounced increase in anodic and cathodic peak potentials (Epa = 0.423 V, Epc = 0.1945 V) and currents (Ipa = 9.867 × 10-5 mA, Ipc = -7.993 × 10-5 mA). In addition, electrochemical impedance spectroscopy (EIS) demonstrated a reduction in charge transfer resistance, which enhanced conductivity. Differential pulse voltammetry (DPV) further showed a linear relationship between current and pesticide concentration, with a high correlation coefficient (R = 0.996), low limit of detection (LOD = 0.0133 mM) and low limit of quantification (LOQ = 0.0405 mM). Real samples, including tap and seawater, were analyzed to validate the method’s applicability. Additionally, chronoamperometry with a step potential of 1.2 V indicated high sensitivity for DiZn detection, with a sensitivity of 0.23 mA mM−1 cm−2. Finally, the stability of the ZnO:SnO2 (1:9) coated GCE was confirmed through recyclability tests over three cycles using CV and DPV techniques, ensuring its robustness for practical applications in pesticide detection.

Carbon Fiber with Superhydrophilic Interface as Metal-free Air Electrode for All-Solid-State Zn-air Batteries

The burgeoning interest in all-solid-state Zn-air batteries as next-generation power sources for portable electronics is conspicuous. A pivotal aspect of their advancement lies in developing cost-effective, metal-free air electrodes with high-activity bifunctional oxygen electrocatalysts. This study introduces a superhydrophilic carbon fiber modified with oxygen functional groups (CF-O), achieved through a straightforward one-step activation treatment. Comparative analyses reveal that the CF-O electrode surpasses pristine CF in oxygen reduction and evolution reaction (OER and ORR) activity due to enhanced active sites and expedited ion transport. Notably, the OER/ORR performance depends on the type and quantity of oxygen functional groups. The optimal CF-O electrode displays an OER overpotential of 365.6 mV at 10 mA cm-2 and an ORR peak potential of 0.683 V. Utilizing the CF-O sample as the air electrode in all-solid-state Zn-air batteries yields an open-circuit voltage of 1.28 V and a peak volume power density of 82.8 mW cm-3. Furthermore, endurance testing reveals a charge/discharge voltage gap of 1.07 V at a current density of 1.0 mA cm-2 after 30 cycles. This facile and economical fabrication approach for metal-free air electrodes holds promise for advancing high-performance metal-air batteries compared to various existing techniques.

Three-component NiO/Fe3O4/rGO nanostructure as an electrode material towards supercapacitor and alcohol electrooxidation

A nanocomposite made of nickel oxide and iron oxide (NiO/Fe3O4) and its hybrid with reduced graphene oxide (rGO) as a conductive substrate with a highly functional surface (NiO/Fe3O4/rGO) was synthesized using a simple hydrothermal approach. This study addresses the challenge of developing efficient materials for energy storage and alcohol fuel cells. After confirming the synthesis through structural analysis, the potential of these nanocomposites as supercapacitor electrodes and catalysts for methanol and ethanol oxidation in alcohol fuel cells were evaluated. The synergy of combining the two metal oxides and adding rGO to the composite structure led to excellent electrocatalytic activity in alcohol oxidation. For the modified NiO/Fe3O4/rGO electrode in the methanol oxidation reaction (MOR), a current density of 450 mA/cm2 at 0.67 V and excellent catalyst stability of 98.7% over 20 hours in chronoamperometric analysis were observed. In the ethanol oxidation reaction (EOR), an oxidative current of 235 mA/cm2 at a peak potential of 0.76 V was seen, with catalyst stability of 96.4% after 20 hours. As a supercapacitor electrode, the NiO/Fe3O4 composite demonstrated a specific capacitance of 946 F/g, while NiO/Fe3O4/rGO showed 1155 F/g. The stability of these electrodes after 10000 GCD cycles was 83.6% and 90.6%, respectively. These findings suggest that the proposed structures are cost-effective and reliable alternatives for energy storage and production, suitable for alcohol fuel cells and supercapacitors.

Theoretical design and synthesis of Co30Ni60/CC for high selective methanol oxidation assisted energy-saving hydrogen production

The integration of methanol oxidation reaction (MOR) with hydrogen evolution reaction (HER) represents an advanced approach to hydrogen production technology. Nonetheless, the rational design and synthesis of bifunctional catalysts for both MOR and HER with exceptional activity, stability and selectivity present formidable challenges. In this work, firstly, density functional theory (DFT) was utilized to design and evaluate material models with high performance for both MOR and HER. Secondly, guided by DFT, Co30Ni60/CC (CC, carbon cloth) composites with a leaf-like nanosheet structure were successfully fabricated via electrodeposition. In the MOR process, Ni acts as the predominant active center, while Co amplifies the electrochemically active surface area (ECSA) and enhances the selectivity of methanol oxidation. Conversely, in the HER process, Co serves as the primary active center, with Ni augmenting the charge transfer rate. The electrochemical results demonstrate that Co30Ni60/CC exhibits exceptional performance in both MOR and HER at a current density (j) of 10 mA cm−2, with peak potentials of 1.323 V and −95 mV, respectively. Additionally, it shows remarkable selectivity for the oxidiation of methanol to high value-added formic acid. Thirdly, following a 100 h chronopotentiometry (CP) test, the required potential demonstrates an increase of 4.9 % (MOR) and 8.1 % (HER), signifying the superior stability of Co30Ni60/CC compared to those reported in the literature. The exceptional performance of Co30Ni60/CC can be primarily attributed to that the leaf-like nanosheets structure not only exposes a plethora of active sites but also facilitates electrolyte diffusion, the monolithic structure prepared by electrodeposition enhances its stability, and the transfer of electrons from Co to Ni regulates its electronic structure, as corroborated by X-ray photoelectron spectroscopy (XPS) and density of states (DOS) analyses. Finally, at the same j, the voltage required by the Co30Ni60/CC||Co30Ni60/CC electrolytic cell, powered by an electrochemical workstation, is 198 mV lower than that required for alkaline water-splitting. Meanwhile, at higher j (100 mA cm−2), the electrolytic cell exhibits sustained and stable operation for 150 h, enabling high-efficiency hydrogen production and the synthesis of high value-added formic acid.

Design of high-performance electrochemical sensor based on SnS2 nanoplates and ionic liquid-modified carbon paste electrode for determination of hydrazine in water samples

Designing effective and accurate analytical techniques to determine hydrazine is essential for preserving the environment. Herein, an electrochemical sensor based on a carbon paste electrode (CPE) modified with SnS2 nanoplates (SnS2NPs) and ionic liquid (IL) was presented for determination of hydrazine in water samples. The SnS2NPs were synthesized using the hydrothermal method and characterized through field emission scanning electron microscope, Fourier transform infrared spectrometer and energy dispersive spectroscopy. The use of cyclic voltammetry in electrochemical investigations has shown that incorporating IL and SnS2NPs in an electrochemical sensor significantly improves its efficiency. These results in a considerable increase in the oxidation peak current and a decrease in the oxidation peak potential of hydrazine compared to an unmodified CPE. The method of differential pulse voltammetry was utilized to accurately measure the quantity of hydrazine. The SnS2NPs/ILCPE showed improved sensing capabilities, resulting in a noticeable sensitivity of 0.0747 µA/µM and a low limit of detection of 0.05 µM for a broad linear range of hydrazine concentration from 0.08 µM to 450.0 µM. In addition, the SnS2NPs/ILCPE sensor was successfully utilized to measure the amount of hydrazine present in water samples, with a recovery range of 96.0 to 104.4 %. The relative standard deviation was found to be lower than 3.6 % (n = 5), indicating that the developed sensor is suitable for accurately determining hydrazine in water samples with high sensitivity.

Reference values for respiratory muscle strength measured with the S‐Index Test in well‐trained athletes, e‐sports athletes and age‐matched controls

AbstractRespiratory function assessment is crucial in optimizing athletic performance, safeguarding respiratory health, and ensuring athletes can perform at their peak potential while minimizing the risk of respiratory‐related issues. The S‐Index Test is a dynamic evaluation of respiratory muscle strength. However, no comprehensive reference values regarding the S‐Index Test have been reported yet. A total of 597 participants performed the S‐Index Test. They were either well‐trained athletes (WTA), or e‐sports athletes (ESA), or age‐matched controls (AMC) groups. The differences in S‐Index Test results between sexes and for group–sex, and performance calibre tier–sex interactions were examined. The relationships between S‐Index Test results and age, anthropometric indices and training experience were assessed. Reference values for all the groups were provided. Amongst athletes, the highest values were observed in swimmers and rowers, and the lowest in figure skaters and runners. The S‐Index Test results were different for the group–sex interaction (P = 0.004, 151.6 ± 29.0 cmH2O for WTA males and 109.8 ± 21.6 cmH2O for WTA females, 136.7 ± 28.0 cmH2O for ESA males and 101.8 ± 22.0 cmH2O for ESA females, 128.7 ± 28.8 cmH2O for AMC males and 70.3 ± 24.7 cmH2O for AMC females) and higher in males than females (P < 0.001, 145.1 ± 30.5 cmH2O for males and 100.8 ± 27.6 cmH2O for females). The higher athletic level, presented as performance calibre tier, was not linked to higher respiratory muscle strength in the WTA group (P = 0.094). However, the Bonferroni correction revealed that except for the singular tier in females, there was a significant effect for all the other tiers and sexes (P < 0.001). The obtained results confirm that regardless of the level of physical activity, the anthropometric features are positively linked with respiratory muscle strength. Furthermore, age and training experience were positively correlated with the S‐Index Test results in the WTA group.

Edifice of metal stannate as nano-catalyst: An ultra-sensitive and highly selective enhanced electrochemical sensing of chloronitrobenzene

Metal stannate is recognized as an effective electrocatalyst in the electrochemical sensor field. In this case, the simple co-precipitation method was used to produce Zn2SnO4. A range of microscopic and spectroscopic techniques were employed to describe the physicochemical properties of synthesized materials. In a modified glassy carbon electrode (GCE), the electrochemical performance of Zn2SnO4 was investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in a three-electrode setup. When reducing 1-chloro-4-nitrobenzene (CNB), Zn2SnO4/GCE exhibits strong electrochemical activity, showing a lower peak potential and a larger cathodic peak current than when GCE is used alone. With a sensitivity of 7.2 nM at the lower detection limit, the linear range response ranges from 0.04 to 360.21 µM. Furthermore, when tested with aromatic nitro groups, inorganic species, and antibiotic therapies, the modified electrode shows good storage stability, reproducibility, repeatability, and interference study capabilities. Zn2SnO4/GCE also demonstrates better electrochemical sensitivity for the detection of CNB. The synthesized Zn2SnO4/GCE exhibits remarkable practical ability to identify CNB in water samples with sufficient yield. This is the first report we are aware of regarding Zn2SnO4/GCE studies of electrochemical sensing towards CNB.

Synthesis, Structural, Electrochemical, and DFT Studies of Highly Substituted Nonplanar Ni(II) Porphyrins and Their Intensity-Dependent Third-Order Nonlinear Optical Properties.

We designed and successfully synthesized highly substituted electron-deficient nonplanar Ni(II) porphyrins and their derivatives (1-7) in moderate to good yields. These derivatives were comprehensively characterized by various spectroscopic techniques and single-crystal X-ray diffraction (SCXRD) analysis. SCXRD analysis confirmed the structures of compounds 2, 4, and 7, adopting saddle-shape geometry. These nonplanar porphyrins demonstrated significant bathochromic shifts in their absorption spectra compared to parent NiTPP, attributed to the influence of bulky β-substituents and/or peripheral fusion. π-Extended porphyrins 6 and 7 displayed panchromatic absorption spectra extending into the NIR region. Porphyrins 6 and 7 demonstrated a profound anodic shift (∼400 mV) in their first reduction peak potentials compared to precursor NiTPP(NO2)Br6. The experimental absorption spectral pattern matches the simulated absorption spectra obtained from TD-DFT studies. The femtosecond laser intensity-dependent third-order nonlinear optical studies revealed that NiDFP(VCN)2Br6 (6) and NiDFP(VCN)2(PE)6 (7) displayed giant optical nonlinearities compared to the other porphyrins. Among all, NiDFP(VCN)2Br6 (6) possessed the highest two-photon absorption coefficient (β) and cross-section (σTPA) values in the range of 22-33 × 10-10 m/W and 3.77-6.95 × 106 GM, respectively. These findings suggest that the investigated nonplanar π-extended porphyrins are promising candidates for future optoelectronic applications.

Surface functionalization of graphene electrode using flavin AuNps for a realtime sensing of asparagine

Asparagine (ASN) is one of the major non-essential amino acids and helps to breakdown the toxic ammonia within the cell. The electrochemical detection of asparagine was performed by the surface functionalized screen-printed carbon (MSPEC) and screen-printed graphene electrodes (MSPEG) through flavin (Quercetin) based gold nanoparticles (AuNps). Cyclic voltammetry (CV) and Differential Pulse Voltammetry (DPV) were performed through MSPEC and MSPEG at single drop of analyte via DROPSENS. SEM and Electrochemical Impedance (EIS) examined for the surface characteristics, enhancement, and functionality of electrodes modified with flavin AuNps. The surface functionalized electrodes revealed excellent electrochemical sensor with high stability, selectivity, repeatability, and have a low limit detection of 0.001 nM. Also, sensors progression was found to occur through adsorption-controlled phenomena. The oxidation peak potential for asparagine in CV and DPV was well-expressed by the MSPEC and MSPEG, with potentials of +0.0881 V and +0.3141 V, respectively. Hence the flavin based AuNps is a new sensing platform for the consistent asparagine real-time sensor and the selective electrochemical detection of asparagine with an exceptionally low detection limit at one drop.

Nuciferine analogs block voltage-gated sodium, calcium and potassium channels to regulate the action potential and treat arrhythmia

Dysfunction of the Nav1.5, Cav1.2, and Kv channels could interfere with the AP and result in arrhythmias and even heart failure. We herein present a novel library of nuciferine analogs that target ion channels for the treatment of arrhythmias. Patch clamp measurements of ventricular myocytes revealed that 6a dramatically blocked both the INa and ICa without altering the currentvoltage relationship (including the activation potential and peak potential), accelerated the inactivation of Nav and Cav channels and delayed the resurrection of these channels after inactivation. Additionally, 6a significantly decreased the APA and RMP without affecting the APD30 or APD50. The IC50 values of 6a against Nav1.5 and Cav1.2 were 4.98 μM and 4.62 μM, respectively. Furthermore, 6a (10 μM) blocked IKs, IK1, and Ito with values of 17.01 %±2.54 %, 9.09 %±2.78 %, and 11.15 %±3.52 %, respectively. Surprisingly, 6a weakly inhibited hERG channels, suggesting a low risk of proarrhythmia. The cytotoxicity evaluation of 6a with the H9c2 cell line indicated that this compound was noncytotoxic. In vivo studies suggested that these novel nuciferine analogs could shorten the time of arrhythmia continuum induced by BaCl2 and normalize the HR, QRS, QT and QTc interval and the R wave amplitude. Moreover, 6a dose-dependently affected aconitine-induced arrhythmias and notably improved the cumulative dosage of aconitine required to evoke VP, VT, VF and CA in rats with aconitine-induced arrhythmia. In conclusion, nuciferine analogs could be promising ion channel blockers that could be further developed into antiarrhythmic agents.

Electrochemical oxidation of ethanol on NiO/MoO2 hybridized wheat husk derived activated carbon

The ethanol oxidation process in fuel cells is most efficient when conducted by platinum based catalysts. Our research team endeavored to find affordable and efficient catalysts, synthesizing catalysts based on metal oxides of nickel and molybdenum in the form of NiO/MoO2and NiO/MoO2hybridized with activated carbon obtained from the wheat husk (ACWH) through a hydrothermal method. After precise physical characterization, the capability of these catalysts in the ethanol oxidation process was measured through electrochemical analyses in an alkaline environment. The presence of ACWH in the catalyst structure significantly improves the active surface and electrocatalytic activity. NiO/MoO2/ACWH with a current density of 16 mA cm-2at a peak potential of 0.55 V and 93% cyclic stability after 5000 alternate CV cycles, can be an appealing, relatively efficient, and stable option in ethanol oxidation.

Supported IrO2 Nanocatalyst with Multilayered Structure for Proton Exchange Membrane Water Electrolysis.

The design of a low-iridium-loading anode catalyst layer with high activity and durability is a key challenge for a proton exchange membrane water electrolyzer (PEMWE). Here, the synthesis of a novel supported IrO2 nanocatalyst with a tri-layered structure, dubbed IrO2@TaOx@TaB that is composed of ultrasmall IrO2 nanoparticles anchored on amorphous TaOx overlayer of TaB nanorods is reported. The composite electrocatalyst shows great activity and stability toward the oxygen evolution reaction (OER) in acid, thanks to its dual-interface structural feature. The electronic interaction in IrO2/TaOx interface can regulate the coverage of surface hydroxyl groups, the Ir3+/ Ir4+ ratio, and the redox peak potential of IrO2 for enhancing OER activity, while the dense TaOx overlayer can prevent further oxidation of TaB substrate and stabilize the IrO2 catalytic layers for improving structural stability during OER. The IrO2@TaOx@TaB can be used to fabricate an anode catalyst layer of PEMWE with an iridium-loading as low as 0.26mgcm-2. The low-iridium-loading PEMWE delivers high current densities at low cell voltages (e.g., 3.9Acm-2@2.0 V), and gives excellent activity retention for more than 1500h at 2.0Acm-2 current density.