Electrochemical Studies Research Articles

Synthesis, Characterization, and Electrochemical Study of Novel Porphyrin Derivatives as Corrosion Inhibitors for Carbon Steel in HCl Solutions

This study involves the synthesis of some porphyrins derivatives, these are termed as 4,4',4'',4'''-(porphyrin-5,10,15,20-tetrayl)tetrakis(N-(6-aminoacridin-3-yl)benzamide) (3a), 4,4',4'',4'''-(porphyrin-5,10,15,20-tetrayl)tetrakis(N-(5-methoxybenzo[d]thiazol-2-yl)benzamide) (3b), 4,4'-(10,20-bis(3-hydroxyphenyl)porphyrin-5,15-diyl)bis(N-(6-aminoacridin-3yl)benzamide) (5a), and 4,4'-(10,20-bis(3-hydroxyphenyl)porphyrin-5,15-diyl)bis(N-(benzo[d]thiazol-2-yl)benzamide) (5b). These derivatives were synthesized using open circuit potential (OCP) and potentiodynamic polarization (PDP) in 0.1 M HCl solution methods. These derivatives were characterized using nuclear magnetic resonance (1H- and 13C-NMR) spectroscopy, mass spectra (ESI), and micro elemental analysis (CHN). The activity of these synthesized materials was investigated as a corrosion inhibitor using carbon steel (CS) as a model for corroded materials. The obtained results showed that the synthesized porphyrins derivatives were effective corrosion inhibitors to 0.1 M HCl solution for CS. In the case of the derivative 3a, a maximum inhibition efficiency (IE%) was recorded and it was around 74%. The derivative 3b showed an IE% of around 68.11%, while the %IE of 5a and 5b were around 18.98% and 45.16%, respectively. The best IE% value that was recorded for the derivative 3a has the potential to be effective anticorrosive coatings for industrial applications and act as mixture inhibitor because their ΔEcorr values are less than 85 mV. On the CS surface following treatment with compound 3a, the inhibitor mechanism for acidic medium (HCl) was investigated.

Electrochemical studies on emulsion coated mild steel in ground water

Electrochemical studies on emulsion coated mild steel in ground water

Synthesis and electrochemical studies of 1,1’-binaphthyl-2,2’-diol for aqueous rechargeable lithium-ion battery applications

The constant increase in the utilization of lithium-ion batteries (LIBs) in various field applications, including electrical vehicles and electronic devices, has led researchers to focus on their multiple path developments to obtain new electrode materials. The practical development of these electrode materials, based on organic and inorganic moieties, is challenging for various groups of LIB scientists. The concept of organic electrode materials is highly competitive with inorganic electrode materials because of the accessibility of more active sites with structural diversity, high energy and power density, environmental friendliness potential sustainability, and low cost. Herein, 1,1’-binaphthyl-2,2’-diol (BINOL) is investigated as an organic electrode material that contains two hydroxyl groups that act as active centers. The oxidative coupling process is employed to synthesize BINOL and so obtained product was characterized by using FT-IR, 1H-NMR and MASS techniques. The electrochemical investigations were carried out using sat. Li2SO4 electrolytic medium at three-electrode cell system. The Cyclic voltammetry (CV) has provided information on the anodic behavior of the material and its stability studied at different scan rates. The battery performance of the cell BINOL | Sat. Li2SO4 | LiMn2O4 by galvanostatic charge-discharge potential limit (GCPL) shows 197/171mAhg−1 specific capacity and 90% columbic efficiency. The electrochemical kinetic obtained by potentiostatic electrochemical impedance spectroscopy (PEIS) shows a semi-infinite diffusion process.

Studying the structure, BSA and FS-DNA interaction, fluorescence sensing of anions, cytotoxicity, and catecholase activity of Cu(II) and Zn(II) Schiff base complexes

Synthesis, characterization, X-ray crystallography, and the interaction with BSA/FS-DNA are reported for two new complexes, [{CuII2L(NCS)2}(μ1,3-NCS)]n (1) and [ZnII2L(μ1,1-N3)(N3)2] (2) (where L=[2,6-bis{N-(2-pyridylethThis section comprises references that occur in the reference list but not in the body of the text. Please position each reference in the text or, alternatively, delete it.yl)formidoyl}-4-methylphenol]). Characterization of the complexes was performed using elemental analysis, UV–vis, and FT-IR spectroscopy. X-ray analysis revealed a thiocyanate-bridged 1-D polymeric structure for complex 1 and a homodinuclear monophenoxo- and azido-bridged structure for complex 2. ‌‌Binding affinity and interaction mode with BSA/FS-DNA were investigated for both complexes using absorption and emission spectroscopy, viscosity measurement, circular dichroism, agarose gel electrophoresis, electrochemical study, and docking simulation. The EtBr replacement experiments clarified an effective binding affinity, Kb = 0.53 × 106 M−1 and Kb = 3.5 × 106 M−1 for complex 1 and 2, respectively, and intercalation as the dominant binding mode for both complexes. Furthermore, the cytotoxicity detection test of the complexes against AGS, MCF-7, PC3 cancer, and NIH/3T3 normal cell lines has shown a moderate selective anticancer activity against MCF-7 and AGS in complex 1. Both complexes triggered apoptosis-programmed cell death. Also, complex 2 showed a sensitive and selective turn-off fluorescence behavior (Kb = 1.1 × 1010 M−1) toward CrO42− among various anions with LOD of 5 × 10−7 M. Moreover, the ability of complex 1 to catalyze the oxidation of 3,5-di‑tert‑butyl catechol (3,5-DTBCH2) to its related quinone, was investigated and it showed an acceptable enzymatic activity.

Investigating the role of corrole as an excitation energy relay in light-induced processes in closely connected N,N'-bis(biphenyl-4-yl)aniline functionalized corrole donor-acceptor dyad.

A photosynthetic antenna-reaction center model, BBA-PFCor comprised of N,N'-bis(biphenyl-4-yl)aniline (BBA) covalently functionalized to bis(pentafluoro)corrole moiety has been prepared and the contribution of the BBA as the photoinduced energy transfer antenna was investigated. UV-visible studies have shown that integrating the electron-rich BBA chromophore into the corrole core has broadened the soret band of the corrole moiety with the absorption spanning from 300 to 700 nm. Electrochemical studies, in corroboration with the computational calculations, revealed that, BBA moiety can act as an electron reservoir and, in the excited state, it would transfer the excited energy to the corrole moiety in the dyad. Steady-state fluorescence studies have demonstrated that, upon photoexcitation of the BBA moiety of BBA-PFCor at 310 nm in solvents of varied polarity, the BBA emission centered at 400 nm was observed to be quenched, with the concomitant appearance of the corrole emission from 500 to 700 nm, indicating the happening of photoinduced energy transfer (PEnT) from 1BBA* to corrole moiety. Parallel control experiments involving the excitation of the corrole moiety at 410 nm did not result in the diminishing of the corrole emission, suggesting that the quenching of the BBA emission in BBA-PFCor is majorly due to intramolecular PEnT from 1BBA* to corrole moiety leading to the formation of singlet excited corrole, that is, 1BBA*-PFCor ➔ BBA-1PFCor*. The free energy changes of PEnT, ΔGEnT, were found to be thermodynamically feasible in all the solvents used for the study. Parallel time-resolved fluorescence studies were congruent with the steady-state fluorescence results and provided further evidence for the occurrence of ultrafast PEnT from 1BBA*➔corrole in the dyad with the rates of energy transfer (kEnT) of ~108 s-1.

Syntheses and reactivities of polymethylated ferrocenes: The effect of methylation upon electrophilic addition

A series of ferrocene derivatives with three, four, five, six and seven methyl group substituents has been prepared and characterized by multinuclear NMR, high resolution mass spectrometry and elemental analyses. Chemical oxidation of heptamethylferrocene with silver tetrafluoroborate produced paramagnetic heptamethylferricenium tetrafluorborate and the structure of one isomer of [C5Me4HFeC5Me3H2][BF4] was determined by single crystal X-ray diffraction. Electrochemical studies of the entire series of iron sandwich compounds from ferrocene to decamethylferrocene reveal a highly linear shift of the reversible half-wave potential (E1/2) for the FeIII/FeII couple such that each additional methyl group lowers E1/2 by an average of 54 mV. A new triple-decker complex has been synthesized by the addition of a ruthenium electrophile, [Cp*Ru(NCMe)3][PF6], (Cp* = C5Me5) to heptamethylferrocene, Me7FcH. While previous work established that reactions between [Cp*Ru(NCMe)3][PF6] and ferrocene derivatives with eight or more methyl group substituents readily form bimetallic complexes, reactions with ferrocene derivatives with six or fewer methyl groups brought about ring abstraction and afforded only monometallic products. Thus it may be concluded that there is a “tipping point” in the series of polymethylated ferrocenes such that the electron donating ability and/or steric influence of seven methyl groups is just sufficient to stabilize a ruthenium-iron tripledecker complex.

In-situ differential electrochemical mass spectrometry study on the effects of negative/positive ratios on gas evolution in lithium-ion full batteries

In-situ differential electrochemical mass spectrometry study on the effects of negative/positive ratios on gas evolution in lithium-ion full batteries

Enzymatic conversion of CO2 to formate: The potential of tungsten-containing formate dehydrogenase in flow reactor system

This study introduces a novel approach for CO2 reduction to formate using the recombinant formate dehydrogenase 1 (MeFDH1) from Methylorubrum extorquens AM1 as biocatalyst, addressing challenges in activity, productivity, and long-term stability of enzyme. We demonstrate that immobilized MeFDH1 supported by electrochemical reaction system enhances formate production and stability, achieving over 1.7 M concentration with an initial rate of 20 mM/h and near-unity Faradaic efficiency for over 200 hours. In further, the reusability of immobilized MeFDH1 was obtained without significant declination of productivity and selectivity. The electrochemical study of MeFDH1 found the product inhibition in continuous CO2 conversion. To overcome this challenge and build efficient process, the integration of a flow reactor system and in-situ separation unit further improved the system's performance and scalability. This advancement in enzymatic CO2 conversion suggests the potential of biocatalysis towards addressing global warming through sustainable chemical synthesis.

Cationic-Surfactant (CTAB) Assisted Preparation of 2D Graphitic Carbon Nitride (g-C3N4) Sheets Advances Supercapacitive Performance

The distinct physicochemical characteristics of metal-free graphitic carbon nitride (g-C3N4) are gaining interest in various fields, including energy storage and conversion. However, the electrochemical performance of this material is constrained, owing to its minimal surface area. Incorporating a surfactant is one of the ways to resolve the issue of surface area and therefore improve the electrochemical performance of g-C3N4. This research delves into a method aimed at improving the supercapacitive capabilities of 2D g-C3N4 sheets through the implementation of a cationic surfactant, cetyltrimethylammonium bromide (CTAB). Electrochemical studies reveal that the CTAB-assisted g-C3N4 sheets exhibit remarkable improvements in specific capacitance, cyclic stability, and comparative rate capability in relation to pristine g-C3N4. The specific capacitance of g-C3N4 with CTAB exceeds about 28%, which gives 162. 8 F g−1. This value is 117.7 F g−1 for electrode material without CTAB at 0.5 mA cm−2. This improved electrochemical performance can be credited to the heightened surface area, improved electronic conductivity, and optimized charge transfer kinetics facilitated by the CTAB surfactant. We aim to emphasize the enhancement of the overall performance of g-C3N4-based supercapacitors for advanced energy storage systems.

Urea–acetamide-based deep eutectic compound as novel, eco-friendly additives in stable and efficient dye-sensitized solar cells: A performance and electrochemical study

Deep eutectic solvents of urea and acetamide at molar ratios of 1:1 (UA11) and 1:2 (UA12) were investigated as new, eco-friendly, and effective electrolyte additive candidates to replace the commonly used 4‑tert-butylpyridine additive in dye-sensitized solar cells (DSCs). Both UA11 and UA12 resulted in a high open circuit potential (VOC) of about 745 mV, which was very competitive to a VOC of 754 mV from DSCs using 4‑tert-butylpyridine (4-TBP). After 2240 h of storage, performance dropped 8% in devices using UA11 compared to about 25% of devices using 4-TBP as an additive. Our time-series data analysis revealed the correlation between the short circuit current (JSC) drop and the increase of counter-electrode resistance. In addition, by examining the VOC correlation between working electrode resistance and working electrode capacitance in four electrolyte groups (NAd, UA11, UA12, 4-TBP), we could speculate the effects of the DES urea-acetamide as well as 4-TBP. 4-TBP could improve the VOC by adsorption to the bare TiO2 surface and diminish the recombination reaction. On the other hand, 4-TBP could interact with iodine species in the electrolyte solution to minimize the current leakage from the TiO2 surface to the iodine species. In the case of UA11 and UA12, the additive seemed to interact with the iodine species only.

Effect of modified titanium dioxide photoanode and agarose gel electrolyte on electrochemical studies of dye-sensitized solar cell

Recently, the study of new DSSC structures such as photoanodes, electrolytes, and counter electrodes (CE) have gained the attention of researchers. Combining these features allows DSSC to have a flexible and versatile way of working. Titanium dioxide-graphene (TiO2-G) nanocomposite containing 3 wt % graphene (G) was successfully fabricated and employed as the photoanode for the fabrication of a dye-sensitized solar cell (DSSC). Agarose (3 wt %) together with potassium iodide (KI) were prepared as gel electrolytes and polyaniline-graphene oxide (PANI-GO) served as the counter electrode (CE). In UV–visible spectroscopy, doping of graphene on TiO2 led to a remarkable reduction of the band gap energy from 3.0 eV (TiO2) to 2.4 eV (TiO2-G). The presence of agarose in the KI solution facilitated the creation of fine channels, promoting ionic transfer in electrolytes, as revealed by field emission scanning electron microscopy (FESEM). Moreover, the current-voltage (I–V) curve for TiO2-G/3 wt % agarose gel electrolyte/PANI-GO demonstrated a power conversion efficiency (PCE) value of 1.1324% with optimal values for short circuit current density (JSC), open circuit voltage (VOC), and fill factor (FF) of 34.48 mA/cm2, 0.1105 V, and 0.2972, respectively. Cyclic voltammetry (CV) illustrated redox potential occurrences at −0.2 V and +0.2 V, corresponding to oxidation and reduction processes, confirming the chemical stability of DSSC. The system demonstrated stability after 10 cycles, maintaining consistent current (μA) and voltage (V) patterns even after 20 cycles. These results demonstrate the efficient and cost-effective DSSC system's capacity to maintain stability and guarantee consistent energy conversion.

Dissociative Electron Transfer to N‐(Arylthio)phthalimides: Factors Affecting the Formation and Dissociation of Radical Anions

AbstractA series of chemically and biologically relevant N‐(arylthio)phthalimides is synthesized and its electrochemical reduction investigated. The results of the electrochemical study are analysed through application of Savéant's dissociative electron transfer theory and with the assistance of theoretical calculations. Reduction of all investigated N‐(arylthio)phthalimides leads to the corresponding radical anions, followed by the ejection of the phthalimide anion resulting from the dissociation of the N−S chemical bond. This stepwise electron transfer mechanism is evidenced by the electrochemical data which allow determination of the standard reduction potentials of all compounds. In the formation of the N‐(arylthio)phthalimide radical anions, the theoretical calculations show that the incoming electron, is hosted by the phthalimidyl group indicating a homolytic dissociation mechanism. The dissociation rate constants of the radical anions are deduced and show that upon changing the substituent from the MeO, to Me, H, F, Cl and Br the dissociation becomes faster. A good correlation with the Hammett substituent constants is also obtained. Application of Savéant's theory through determination of the associated driving force and the intrinsic barrier energies help rationalize the observed results and show that the change in the dissociation rate constant depends mainly on the standard reduction potential of the parent compounds.

Microwave-assisted synthesis, photochemical and electrochemical studies of long-wavelength BODIPY dyes

Novel BODIPY derivatives possessing different styryl substituents were synthesized using different methods of Knoevenagel-type condensation with conventional heating and microwave radiation in two conditions. Microwave-assisted synthesis significantly reduces reaction time while enhancing its efficiency. The introduction of styryl substituents at the 3 and 5 positions of the BODIPY core resulted in a substantial bathochromic shift, which was affected by the substituents within styryl groups. Depending on the solvents, the BODIPY with unsubstituted styryl groups possesses absorption maxima (λAbs) between 616 and 626 nm. While the analogs containing electron-donating methoxy and methylthio groups exhibited bathochromically shifted bands with λAbs values in the 633-654 nm range. Fluorescence studies revealed intensive emission of tested BODIPYs with fluorescence quantum yields at the 0.41-0.83 range. On the other hand, singlet oxygen quantum yields were very low. In the electrochemical studies, the CV and DPV scans showed the presence of three redox processes. The calculated electrochemical gaps were in the range of 1.71-1.87 V.

Investigating oxidant-catalyst interactions in the persulfate system: Implications for efficient removal of phenolics and antibiotics

Persulfate (PS) activation by carbon catalyst holds both scientific and practical significance to curb the toxicity effects of organic pollutants in the natural water environment. Here, we investigated a relatively unfamiliar characteristics (i.e., oxidant-catalyst interaction) that influence the removal efficiency in PS activated system, utilizing N-doped mesoporous carbon hollow spheres (N-MCHS; size ∼385 nm) as a catalyst. The selection of this catalyst was motivated by its desired physicochemical characteristics such as high dispersibility, uniformly distributed pores and high specific surface area (1109 m2 g−1) for catalytic application. The removal performance was studied by degrading bisphenol A at very low PS (0.25 mM) and catalyst (10.0 mg L−1) concentrations. Through this study, we established a correlation between the surface charge of N-MCHS and PS interaction on the catalytic performance. Further, electron spin resonance (ESR) and radical scavenger studies were carryout out to prove the nonradical oxidation process. Electrochemical studies provided a strong evidence for PS complexation and electron transfer during oxidative removal of bisphenol A. Additional studies with different phenolics and antibiotics demonstrated that N-doping significantly accelerates the degradation rate and enhances the removal efficiency. The results of present study unveil the potential use of PS+N-MCHS in the degradation of different organic contaminants at low catalyst dosages.

Computational, spectroscopic, sensor and biological studies of Cu(II) complex of Fluoro substituted Schiff base

Schiff base ligand (FHPB - 2-[N-(fluorophenyl)-4‑hydroxy-4-phenyl] 3-butene), and its copper complex Cu[FHPB]2 were prepared and the structural framework of prepared compounds were characterized by analytical, spectroscopic and DFT calculation techniques. The result suggests that, prepared Cu[FPB]2 complex possesses square planar geometry. Electrochemical studies reveal that Cu[FPB]2 complex is quasi reversible in nature. Sensing ability of prepared ligand with various cations were analyzed by absorption and emission spectral techniques and infer that the ligand FHPB is highly sensitive and selective sensor for the Cu2+ ion as compared to other selected metal ions. Antimicrobial activities of FHPB and Cu[FPB]2 against selected bacterial and fungal strains were checked by Disc Diffusion method. DNA interaction of prepared compounds were analyzed by spectrophotometric and spectrofluorometric techniques. The analysis illustrates that the synthesized compounds interact with calf thymus DNA by the way of an intercalation mode. Moreover, the binding ability of FHPB and Cu[FPB]2 were demonstrated by molecular docking and it evidences the strong binding with CT-DNA double helix.

Abstract 7289: PancreaAlert: Intelligent nanoengineered biosensor for pancreatic cancer

Abstract Introduction: Pancreatic cancer accounts for 3% of cancer cases and 7% of cancer deaths in the United States. It is currently in the third position with respect to cancer-related deaths, and it is expected to move to second place as of 2040. This is mainly due to its diagnosis in the later stage. If detected in the first or second stage surgery can be performed thus increasing the patient’s survival rate. The current methods of diagnosis cannot do early stage or asymptomatic detection. So, detecting cancer-specific biomarkers can aid in the prognosis. Serum protein-based biomarkers carbohydrate antigen CA242, CA19-9, and carcinoembryonic antigen CEA are specific to pancreatic cancer. Thus, in this preliminary study, we aim to develop a nanoengineered electrochemical biosensor combined with machine learning to detect pancreatic cancer-specific biomarkers CA242, CA19-9, and CEA. Methodology: Nanoengineering the biosensor: The gold working electrode of the gold- biosensor (DRP-250AT) was coated with graphene oxide nano colloidal solution and kept in UV overnight for the graphene oxide nanosheet to crosslink with the working electrode. Detection of biomarkers using an electrochemical biosensor: First, a Crosslinker (DSP) was added to ethanol cleaned biosensor to bind the analytes. Following that antibody specific to each biomarker were added to the biosensors. The addition of TBS superblock prevented non-specific binding. Then different concentrations of biomarkers were added, and the corresponding sensor was subjected to various electrochemical analyses such as electrochemical impedance spectroscopy and voltammetry. SEM-EDAX analysis: The antigen-antibody binding on the biosensor's surface was confirmed. Automation and machine learning: Python code was developed to automate the analysis process and machine learning models (support vector machine and neural network) were used to classify the concentrations into various risk levels. The sensitivity of the developed tool was high when compared with conventional methods like ELISA and confocal microscopy. Results: From the electrochemical studies we found that with increasing concentration of biomarkers, there was a trend in output parameters: capacitance, resistance, impedance and area under the curve. By analyzing this trend, the concentrations of biomarkers can be detected. Using this data as input the machine learning model (accuracy greater than 80%) classified the concentrations into risk levels (normal, low risk, and high risk). Significance: Nanoengineering with graphene oxide nanosheets enhances the sensitivity of electrochemical biosensors. Automation and machine learning models help in the analysis of large datasets produced by this sensor. Overall, this device aids in the prognosis of pancreatic cancer. Our preliminary results are encouraging but more thorough research is required to make this diagnostic tool a working application. Citation Format: Meenal Karunanidhi, Hemalatha Kanniyappan, Edith Zhan, Ruth Mathew, Yani Sun, Junyi Wu, Yan Yan, Gnanasekar Munirathinum, Mathew T. Mathew. PancreaAlert: Intelligent nanoengineered biosensor for pancreatic cancer [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2024; Part 1 (Regular Abstracts); 2024 Apr 5-10; San Diego, CA. Philadelphia (PA): AACR; Cancer Res 2024;84(6_Suppl):Abstract nr 7289.

A theoretical approach to the corrosion inhibition of iron in acidic solution by a green formulation derived from Nigella sativa L seeds oil

A theoretical approach combining density functional theory (DFT) computation, Monte Carlo (MC) methods, and molecular dynamics (MD) simulations was used to investigate and validate the iron corrosion inhibition performances in the acidic medium of a green formulation based on the oil extracted from Nigella sativa L. DFT calculations allowed to determine the energetic, global, and local chemical reactivity parameters. The most stable adsorption configuration of the fatty acids components of the Nigella sativa L. formulation was determined by the Monte Carlo methods with the adsorption locator module and by molecular dynamics simulations. Results indicated that all the compounds are absorbed with a totally flat orientation on the first layer of the metal surface.The active sites of molecules were effectively established by using DFT through the analysis of frontier molecular orbitals (FMO), the Hirshfeld population analysis (HPA), the electrostatic potential (ESP), molecular electron density analysis (MED), and Fukui indices (FI). The solvent effect was investigated by using the conductor-like polarizable continuum model (CPCM). Protonation effects were also analysed through the protonation energy (PE), the proton affinity (PA), and the absolute gas phase basicity (GB). The formation of a coating on the iron surface validated the good protective action of the green formulation derived from Nigella sativa L.The computational and theoretical approaches substantiate our experimental electrochemical and spectroscopic studies [1].

Metal-Free Electrocatalytic Synthesis of Fused Azabicycles from N-Allyl Enamine Carboxylates.

An electrocatalytic approach to access structurally significant azabicyclic scaffolds from N-allyl enamine carboxylates is illustrated. This metal-free method functions exclusively with a catalytic amount of iodide, strategically employed to electrochemically generate a reactive hypervalent iodine species, which facilitates the cascade bicyclization processes with enhanced precision and efficiency. Excellent functional group compatibility was observed, enabling the synthesis of a series of azabicycle derivatives. Detailed mechanistic and electrochemical studies enhance the comprehension of the reaction sequence.

Driving inward growth of lithium metal in hollow microcapsule hosts by heteroatom‐controlled nucleation

AbstractThe application of Li metal anodes in rechargeable batteries is impeded by safety issues arising from the severe volume changes and formation of dendritic Li deposits. Three‐dimensional hollow carbon is receiving increasing attention as a host material capable of accommodating Li metal inside its cavity; however, uncontrollable and nonuniform deposition of Li remains a challenge. In this study, we synthesize metal–organic framework‐derived carbon microcapsules with heteroatom clusters (Zn and Ag) on the capsule walls and it is demonstrated that Ag‐assisted nucleation of Li metal alters the outward‐to‐inward growth in the microcapsule host. Zn‐incorporated microcapsules are prepared via chemical etching of zeolitic imidazole framework‐8 polyhedra and are subsequently decorated with Ag by a galvanic displacement reaction between Ag+ and metallic Zn. Galvanically introduced Ag significantly reduces the energy barrier and increases the reaction rate for Li nucleation in the microcapsule host upon Li plating. Through combined electrochemical, microstructural, and computational studies, we verify the beneficial role of Ag‐assisted Li nucleation in facilitating inward growth inside the cavity of the microcapsule host and, in turn, enhancing electrochemical performance. This study provides new insights into the design of reversible host materials for practical Li metal batteries.

Diruthenium complexes incorporating carboxylated chalcones with phenyl or ferrocenyl units: Synthesis, structural, electrochemical and DNA binding studies

A total of eight diruthenium sawhorse and cationic complexes incorporating carboxylated chalcones with phenyl or ferrocenyl units have been synthesized and characterized. The electrochemical behavior of the sawhorse and cationic complexes incorporating the ferrocenyl moiety have been studied by cyclic voltammetry. For the cationic complexes both the diruthenium core and the ferrocenyl unit undergo oxidation, in contrast only the ferrocenyl moieties for the sawhorse complexes were oxidized. The enhanced solubility of the cationic complexes over the neutral sawhorse compounds in aqueous medium enabled DNA binding studies to be undertaken for the former. All of the cationic complexes could bind to DNA, and displayed better selectivity for quadruplex over duplex DNA. These results indicate that diruthenium cationic complexes are able to bind to quadruplex DNA and have the potential to function as telomerase inhibitors.